JPWO2017099102A1 - Dry-curing gypsum composition for coating material, gypsum-based coating material, and method for applying gypsum-based coating material - Google Patents

Dry-curing gypsum composition for coating material, gypsum-based coating material, and method for applying gypsum-based coating material Download PDF

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JPWO2017099102A1
JPWO2017099102A1 JP2017555088A JP2017555088A JPWO2017099102A1 JP WO2017099102 A1 JPWO2017099102 A1 JP WO2017099102A1 JP 2017555088 A JP2017555088 A JP 2017555088A JP 2017555088 A JP2017555088 A JP 2017555088A JP WO2017099102 A1 JPWO2017099102 A1 JP WO2017099102A1
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gypsum
coating material
composition
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parts
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JP6735290B2 (en
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横山　至
至 横山
嘉一 田中
嘉一 田中
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Yoshino Gypsum Co Ltd
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Abstract

水を加えて石膏系塗材としたときに、薄く平滑でありながら、色ムラが抑制された塗膜を形成することが可能な乾燥硬化形の塗材用石膏組成物を提供する。
平均粒子径が５０μｍ以下の半水石膏と、平均粒子径が５０μｍ以下の炭酸カルシウムと、凝結遅延剤と、を含有し、前記半水石膏１００質量部に対して、前記炭酸カルシウムの含有量が１０〜４００質量部であり、前記凝結遅延剤の含有量が０．１質量部以上である、乾燥硬化形の塗材用石膏組成物を提供する。Disclosed is a dry-curing gypsum composition for coating material, which is capable of forming a coating film that is thin and smooth and has suppressed color unevenness when water is added to form a gypsum-based coating material.
It contains hemihydrate gypsum having an average particle size of 50 μm or less, calcium carbonate having an average particle size of 50 μm or less, and a setting retarder, and the content of calcium carbonate is 100 parts by mass of the hemihydrate gypsum. Provided is a dry-curing gypsum composition for coating material, which is 10 to 400 parts by mass and the content of the setting retarder is 0.1 parts by mass or more.

Description

本発明は、乾燥硬化形の塗材用石膏組成物、石膏系塗材、及び石膏系塗材の施工方法に関する。   The present invention relates to a dry-curing gypsum composition for a coating material, a gypsum-based coating material, and a method for applying a gypsum-based coating material.

建造物の壁、床、及び天井などの表面に塗り壁材などの塗材で塗膜を形成する工法として湿式工法が知られている。湿式工法では、モルタル、漆喰、石膏、又は珪藻土などの無機系粉末を主材とした組成物に水を混練してスラリー状の湿式塗材とし、その湿式塗材を建造物の内装や外装の壁などの表面に鏝で塗る（鏝塗り）などの方法で塗膜を形成することが行われている。特に建造物の内装壁や外装壁の仕上げ塗材においては、壁面の意匠性を確保するために漆喰系塗材や石膏系塗材が広く用いられている。これらの湿式塗材は、一般的に、粉末状の組成物として製品化され、施工現場にて水と混練されて用いられている。   A wet method is known as a method of forming a coating film with a coating material such as a coating wall material on the surface of a wall, floor, or ceiling of a building. In the wet method, water is kneaded into a composition mainly composed of inorganic powder such as mortar, plaster, gypsum, or diatomaceous earth to form a slurry-like wet coating material, and the wet coating material is used for the interior and exterior of a building. Forming a coating film by a method such as painting on a surface such as a wall with a candy (glazing) has been performed. In particular, in finishing coating materials for interior walls and exterior walls of buildings, plaster-based coating materials and plaster-based coating materials are widely used to ensure the design of the wall surfaces. These wet coating materials are generally commercialized as a powdery composition and used by being kneaded with water at a construction site.

例えば、特許文献１には、塗膜形成に石灰、白色顔料、着色顔料、結合剤及び水を含有する着色漆喰組成物を用いることを特徴とする、着色漆喰塗膜の色飛びを抑制する方法が開示されている。特許文献２には、粒径が０．１ｍｍ以下の無機質粉体、粒径０．１ｍｍ以下の石膏、線径５〜１５μｍかつ長さ３〜１０ｍｍの繊維、水溶性糊料、及び合成樹脂をそれぞれ所定の割合で配合した壁面用塗材が開示されている。特許文献３には、半水石膏及び顔料、並びに所定の含有割合にて特定の媒晶剤を含有し、半水石膏が水和した際の二水石膏が、アスペクト比１〜９の板状結晶となるようにコントロールされた乾燥石膏組成物及び石膏系塗材に関する発明が開示されている。   For example, Patent Document 1 uses a colored plaster composition containing lime, a white pigment, a color pigment, a binder, and water for forming a coating film, and a method for suppressing color jump of a colored plaster coating film Is disclosed. Patent Document 2 includes inorganic powder having a particle size of 0.1 mm or less, gypsum having a particle size of 0.1 mm or less, fibers having a wire diameter of 5 to 15 μm and a length of 3 to 10 mm, a water-soluble paste, and a synthetic resin. A coating material for a wall surface that is blended at a predetermined ratio is disclosed. In Patent Document 3, hemihydrate gypsum and pigment, and a specific crystal clearing agent at a predetermined content ratio, the dihydrate gypsum when the hemihydrate gypsum is hydrated are plate-shaped with an aspect ratio of 1 to 9 An invention relating to a dry gypsum composition and a gypsum-based coating material that are controlled to be crystals is disclosed.

特開２００４−３１５３６３号公報JP 2004-315363 A 特開２００９−２４９２７１号公報JP 2009-249271 A 国際公開第２０１２／０７７５２３号International Publication No. 2012/077523

特許文献２にも記載されているように、漆喰系塗材を壁面に鏝塗りする工法は平滑な面に仕上げやすい。したがって、塗材を薄塗りで、具体的には例えば塗り厚が３ｍｍ以下であるような薄塗りで、平滑な塗膜を形成する場合には、石膏系塗材よりも漆喰系塗材を用いることが一般的である。   As described in Patent Document 2, the method of applying a plaster-based coating material to a wall surface is easy to finish on a smooth surface. Therefore, when the coating material is thinly coated, specifically when the coating thickness is 3 mm or less and a smooth coating film is formed, the plaster-based coating material is used rather than the gypsum-based coating material. It is common.

しかし、漆喰系塗材を用いる場合、漆喰はｐＨが塩基性の領域にあり、また、漆喰系塗材を塗布する作業中に粉塵が舞うこともあることから、作業者の安全性を考慮すると、より注意深く作業を行う必要がある。一方、ｐＨを中性付近に調製しやすく上述した安全性の観点からの利点があること、また、クロス（壁紙）や石膏ボードなどの下地に対して付着しやすいことなどから、石膏系塗材を用いる利点がある。   However, when using a plaster-based coating material, the plaster is in a basic pH range, and dust may fly during the operation of applying the plaster-based coating material. Need to work more carefully. On the other hand, it is easy to adjust the pH to near neutral, and has the advantages from the viewpoint of safety described above, and because it easily adheres to the ground such as cloth (wallpaper) and gypsum board, gypsum-based coating materials There is an advantage of using.

しかしながら、本発明者らの検討の結果、半水石膏が水和反応する、いわゆる反応硬化形の石膏系塗材を用いて、例えば塗り厚が３ｍｍ以下であるような薄塗りを行うと、石膏系塗材の硬化によって形成された塗膜において、色ムラが発生しやすい傾向にあることが分かった。   However, as a result of the study by the present inventors, when a thin coating such as a coating thickness of 3 mm or less is performed using a so-called reaction-cured gypsum coating material in which hemihydrate gypsum hydrates, gypsum It was found that color unevenness tends to occur in the coating film formed by curing the coating material.

そこで、本発明は、水を加えて石膏系塗材としたときに、薄く平滑でありながら、色ムラが抑制された塗膜を形成することが可能な乾燥硬化形の塗材用石膏組成物を提供しようとするものである。   Therefore, the present invention provides a dry-cured gypsum composition for coating materials that can form a coating film that is thin and smooth while suppressing color unevenness when water is added to form a gypsum-based coating material. Is to provide.

石膏系塗材で薄塗りを行った場合の塗膜形成の過程は、塗材中の半水石膏が水和反応して硬化する過程のほか、潜在的に塗材中の水分が下地である被着体に吸収され、または、空気中に蒸発することで乾燥して硬化する過程の両方を伴う。塗材中の半水石膏が水和反応する前に、塗材中の水分が下地である被着体に吸収され、または、空気中に蒸発することで半水石膏の水和反応に必要な水分が不足すると、石膏系塗材の硬化によって形成される塗膜に未反応な半水石膏が残る、いわゆるドライアウトが発生しやすいと考えられる。本発明者らは、このドライアウトによって半水石膏が部分的又は不均一に水和反応して形成された塗膜において、半水石膏の未反応部分（ドライアウト部分）と反応部分との間で上述の色ムラが発生するものと考えた。   In the case of thin coating with gypsum-based coating materials, the coating film formation process is not only the process of hydration reaction of the hemihydrate gypsum in the coating material, but also the water in the coating material is potentially the base It involves both a process of being dried and cured by being absorbed by the adherend or evaporating into the air. Before the half-water gypsum in the coating material undergoes a hydration reaction, the moisture in the coating material is absorbed by the adherend that is the base, or is evaporated into the air, which is necessary for the hydration reaction of the half-water gypsum. If the water is insufficient, it is considered that unreacted hemihydrate gypsum remains in the coating film formed by the curing of the gypsum-based coating material, so-called dry out is likely to occur. In the coating film formed by hydration reaction of hemihydrate gypsum partially or non-uniformly by this dry-out, the present inventors made a difference between the unreacted portion (dry-out portion) of the hemihydrate gypsum and the reaction portion. Therefore, it was considered that the above-described color unevenness occurred.

そこで、本発明者らは、従来の石膏系塗材において技術常識的に考えられていた半水石膏の水和反応によって硬化膜を形成する反応硬化形の手法からは発想を転換し、あえて半水石膏の水和反応を生じ難くすることを検討した。そして、本発明者らは、半水石膏の水和反応が生じ難いように構成した石膏組成物に水を加えた石膏系塗材を用いたところ、その石膏系塗材から石膏系塗材の硬化によって形成される塗膜において、意外にも色ムラが抑制される傾向にあることを見出し、本発明を完成するに至った。   Therefore, the present inventors changed the way of thinking from the reaction-curing method of forming a cured film by the hydration reaction of hemihydrate gypsum, which has been considered in the common sense of technology in conventional gypsum-based coating materials. We examined how to make the hydration reaction of water gypsum less likely to occur. And when the present inventors used a gypsum-based coating material in which water was added to a gypsum composition configured so that the hydration reaction of hemihydrate gypsum hardly occurs, the gypsum-based coating material was changed from the gypsum-based coating material. In the coating film formed by curing, the present inventors have found that the color unevenness tends to be suppressed unexpectedly, and have completed the present invention.

本発明は、平均粒子径が５０μｍ以下の半水石膏と、平均粒子径が５０μｍ以下の炭酸カルシウムと、凝結遅延剤と、を含有し、前記半水石膏１００質量部に対して、前記炭酸カルシウムの含有量が１０〜４００質量部であり、前記凝結遅延剤の含有量が０．１質量部以上である、乾燥硬化形の塗材用石膏組成物を提供する。   The present invention comprises hemihydrate gypsum having an average particle size of 50 μm or less, calcium carbonate having an average particle size of 50 μm or less, and a setting retarder, and the calcium carbonate is added to 100 parts by mass of the hemihydrate gypsum. The dry-curing gypsum composition for coating material is provided, wherein the content of is set to 10 to 400 parts by mass and the content of the setting retarder is 0.1 parts by mass or more.

本発明によれば、水を加えて石膏系塗材としたときに、薄く平滑でありながら、色ムラが抑制された塗膜を形成することが可能な乾燥硬化形の塗材用石膏組成物を提供することができる。   According to the present invention, when a gypsum-based coating material is formed by adding water, a dry-cured gypsum composition for coating material that is capable of forming a coating film that is thin and smooth but has suppressed color unevenness. Can be provided.

図１は、試験体２における石膏系塗膜の粉末Ｘ線回折パターンである。FIG. 1 is a powder X-ray diffraction pattern of a gypsum-based coating film in the test body 2. 図２は、試験体１２における石膏系塗膜の粉末Ｘ線回折パターンである。FIG. 2 is a powder X-ray diffraction pattern of the gypsum-based coating film in the test body 12.

以下、本発明の実施の形態について説明するが、本発明は以下の実施の形態に限定されるものではない。   Embodiments of the present invention will be described below, but the present invention is not limited to the following embodiments.

＜塗材用石膏組成物＞
上述の通り、本発明者らの検討の結果、半水石膏を含有する反応硬化形の石膏系塗材を用いて、塗り厚が３ｍｍ以下の薄塗りを行うと、色ムラのある塗膜が形成されやすくなることが分かった。本発明者らは、色ムラの原因について検討したところ、薄塗りであるが故に、塗材中の水分が下地である被着体に吸収され、または、水分が空気中へ蒸発することで、石膏系塗材の硬化によって形成される塗膜に未反応な半水石膏が残るドライアウトが発生しやすいためであると考えた。このドライアウトによって、半水石膏が部分的又は不均一に水和反応して形成された塗膜において、半水石膏の未反応部分（ドライアウト部分）と反応部分との間で上述の色ムラが発生するものと考えられる。
これは、上述の色ムラは、塗材用石膏組成物に水を加えて石膏系塗材とした場合に、塗材中の水分が下地である被着体に吸収されるか、水分が空気中へ蒸発することで塗材の乾燥硬化が完了する時間（以下、「乾燥硬化の完了時間」ともいう）よりも、塗材中の半水石膏の水和反応の始発時間が早い石膏組成物である場合に発生しうると考えられる。<Gypsum composition for coating material>
As described above, as a result of the examination by the present inventors, when a thin coating with a coating thickness of 3 mm or less is performed using a reaction-curing gypsum-based coating material containing hemihydrate gypsum, a coating film with uneven color is obtained. It turns out that it becomes easy to form. As a result of examining the cause of color unevenness, the present inventors have absorbed the moisture in the coating material to the adherend that is the base, or the water evaporates into the air, because it is a thin coating. It was thought that it was because dry out that unreacted hemihydrate gypsum remained on the coating film formed by curing the gypsum coating material was likely to occur. In the coating film formed by hydration reaction of hemihydrate gypsum partially or non-uniformly by this dry-out, the above-mentioned color unevenness between the unreacted portion (dry-out portion) of the hemihydrate gypsum and the reaction portion. Is considered to occur.
This is because the above-mentioned color unevenness is caused when water is added to the gypsum composition for coating material to form a gypsum-based coating material, or moisture in the coating material is absorbed by the adherend as a base, or moisture is air. A gypsum composition in which the initial time of the hydration reaction of hemihydrate gypsum in the coating material is earlier than the time required for the drying and curing of the coating material to complete by evaporating into the coating material (hereinafter also referred to as “dry curing completion time”) It is considered that this can occur when

従来、石膏系塗材は、下地への付着性や塗膜の強度を考慮して、半水石膏に水を加えることで水和反応を生じさせ、半水石膏が二水石膏へと相変化して硬化する反応硬化形の塗材として用いられてきた。しかし、本発明者らは、従来の石膏系塗材において技術常識的に考えられていた反応硬化形の手法から発想を転換し、あえて半水石膏の水和反応を生じ難くすることを検討し、半水石膏の水和反応が生じ難いように構成した石膏組成物を用いることを試みた。その結果、その石膏組成物に水を加えた石膏系塗材によって、意外にも、下地に対して十分な付着性を示し、かつ、色ムラが抑制された塗膜を形成することが可能であることが判明した。
なお、本明細書において、半水石膏の水和反応を生じ難いように構成した石膏組成物とは、当該石膏組成物に水を加えて石膏系塗材とした場合に、半水石膏の水和反応の始発時間よりも、塗材中の水分が下地である被着体に吸収され、または、水分が空気中へも蒸発し、塗材の乾燥硬化の完了時間がより早い石膏組成物であることを意味する。乾燥硬化の完了時間が水和反応の始発時間よりも早い場合、水和反応のために必要な量の水分が周囲に存在しないため、水和反応が抑制される。Conventionally, gypsum-based coating materials have a hydration reaction by adding water to hemihydrate gypsum in consideration of adhesion to the base and the strength of the coating film, and the phase change from hemihydrate gypsum to dihydrate gypsum. It has been used as a reaction-curing coating material that cures. However, the present inventors have changed the idea from the reaction-curing type method that has been considered in the common sense in conventional gypsum-based coating materials, and dared to make it difficult to cause the hydration reaction of hemihydrate gypsum. An attempt was made to use a gypsum composition configured so that the hydration reaction of hemihydrate gypsum hardly occurs. As a result, the gypsum-based coating material obtained by adding water to the gypsum composition can unexpectedly form a coating film that exhibits sufficient adhesion to the base and has suppressed color unevenness. It turned out to be.
In the present specification, the gypsum composition configured so as not to easily cause the hydration reaction of hemihydrate gypsum refers to the water of hemihydrate gypsum when water is added to the gypsum composition to form a gypsum-based coating material. A gypsum composition in which the moisture in the coating material is absorbed by the adherend that is the base, or the moisture evaporates into the air, and the completion time of drying and curing of the coating material is earlier than the initial time of the sum reaction. It means that there is. When the completion time of the drying and curing is earlier than the initial time of the hydration reaction, the amount of water necessary for the hydration reaction does not exist in the surrounding area, and thus the hydration reaction is suppressed.

すなわち、本発明の一実施形態の塗材用石膏組成物（以下、単に「石膏組成物」ということがある）は、平均粒子径が５０μｍ以下の半水石膏と、平均粒子径が５０μｍ以下の炭酸カルシウムと、凝結遅延剤と、を含有する。この石膏組成物では、半水石膏１００質量部に対して、炭酸カルシウムの含有量が１０〜４００質量部であり、凝結遅延剤の含有量が０．１質量部以上である。そして、この石膏組成物は、乾燥硬化形の石膏系塗材に用いられるものである。   That is, the gypsum composition for a coating material according to an embodiment of the present invention (hereinafter sometimes simply referred to as “gypsum composition”) has a half-water gypsum having an average particle size of 50 μm or less and an average particle size of 50 μm or less. Contains calcium carbonate and a set retarder. In this gypsum composition, the content of calcium carbonate is 10 to 400 parts by mass and the content of the setting retarder is 0.1 parts by mass or more with respect to 100 parts by mass of hemihydrate gypsum. The gypsum composition is used for a dry-curing gypsum-based coating material.

本実施形態の石膏組成物は、水を含有する石膏系塗材として好適に用いられる。その石膏組成物は、石膏組成物に水を加えて石膏系塗材としたときに、その石膏系塗材によって塗膜を形成することが可能なものであり、より具体的には、その石膏系塗材を被着体に塗布し、乾燥硬化させることで、塗膜を形成することが可能なものである。   The gypsum composition of this embodiment is suitably used as a gypsum-based coating material containing water. The gypsum composition can form a coating film with the gypsum-based coating material when water is added to the gypsum composition, and more specifically, the gypsum composition. A coating film can be formed by applying a system coating material to an adherend and drying and curing it.

石膏組成物は、平均粒子径が５０μｍ以下である半水石膏及び炭酸カルシウム、並びに凝結遅延剤を特定量にて含有するため、薄く平滑で、表面硬度の高い塗膜を形成することが可能である。よって、石膏組成物に水を加えて調製される石膏系塗材を用いることで、引っ掻き傷や衝撃に対する耐性が良好な塗膜を形成することが可能である。したがって、石膏組成物を用いて調製される石膏系塗材を、例えば壁面に塗布して乾燥硬化させ、塗膜を形成させれば、引っ掻き傷や衝撃に対する耐性が良好な壁面を形成することができる。なお、石膏組成物によって、薄く平滑でありながら表面硬度の高い塗膜を形成することが可能であることは、平均粒子径がともに５０μｍ以下である半水石膏と炭酸カルシウムとが特定の割合で含有されることで、それらが相乗的に作用することによるものと推察される。   Since the gypsum composition contains hemihydrate gypsum and calcium carbonate having an average particle diameter of 50 μm or less and a setting retarder in specific amounts, it is possible to form a thin and smooth coating film with high surface hardness. is there. Therefore, by using a gypsum-based coating material prepared by adding water to the gypsum composition, it is possible to form a coating film having good resistance to scratches and impacts. Therefore, if a gypsum-based coating material prepared using a gypsum composition is applied to a wall surface, for example, dried and cured to form a coating film, a wall surface having good resistance to scratches and impacts can be formed. it can. In addition, it is possible to form a coating film having a high surface hardness while being thin and smooth by using the gypsum composition. The reason is that hemihydrate gypsum and calcium carbonate both having an average particle diameter of 50 μm or less are in a specific ratio. By containing, it is guessed that they act synergistically.

さらに、本実施形態の石膏組成物は、半水石膏１００質量部に対して、凝結遅延剤を０．１質量部以上含有するため、石膏組成物中の半水石膏の水和反応が抑制される。そのため、本実施形態の石膏組成物を用いることで、半水石膏の部分的又は不均一な水和反応を抑制することができ、ほぼ全体的又はほぼ均一に半水石膏が維持された塗膜を形成することが可能である。よって、本実施形態の石膏組成物によって、薄く平滑な塗膜でありながら、半水石膏の部分的又は不均一な水和反応に起因した色ムラを抑制することができる。   Furthermore, since the gypsum composition of this embodiment contains 0.1 mass part or more of a setting retarder with respect to 100 parts by mass of hemihydrate gypsum, the hydration reaction of hemihydrate gypsum in the gypsum composition is suppressed. The Therefore, by using the gypsum composition of the present embodiment, partial or non-uniform hydration reaction of hemihydrate gypsum can be suppressed, and the coating film in which hemihydrate gypsum is maintained almost entirely or substantially uniformly. Can be formed. Therefore, the gypsum composition of this embodiment can suppress color unevenness due to partial or non-uniform hydration reaction of hemihydrate gypsum while being a thin and smooth coating film.

本実施形態の石膏組成物は、上述の通り、水が加えられた際に、石膏組成物中の半水石膏の水和反応が抑制されるように、好ましくは前記水和反応が生じないように、構成されている。この構成は、次に述べるように、Ｘ線回折による構造解析や水和反応の始発時間によって規定することもできる。   As described above, the gypsum composition of this embodiment preferably does not cause the hydration reaction so that the hydration reaction of hemihydrate gypsum in the gypsum composition is suppressed when water is added. It is configured. As described below, this configuration can also be defined by structural analysis by X-ray diffraction or the initial time of the hydration reaction.

半水石膏（ＣａＳＯ4・１／２Ｈ2Ｏ）が水和反応を起こすと二水石膏（ＣａＳＯ4・２Ｈ2Ｏ）に変化する。Ｘ線回折パターンにおいて、二水石膏は回折角１１〜１２°に明瞭な回折ピークが表れ、半水石膏は回折角１４〜１５°に明瞭な回折ピークが表れることが知られている。この既知情報と、石膏組成物と水との混練物を塗布し、硬化させた塗膜の粉末Ｘ線回折から、石膏組成物が、石膏組成物中の半水石膏の水和反応が抑制されるように（好ましくはその水和反応の始発時間が乾燥硬化の完了時間よりも遅くなるように）構成されているか否かを確認することが可能である。When hemihydrate gypsum (CaSO 4 .1 / 2H 2 O) undergoes a hydration reaction, it changes to dihydrate gypsum (CaSO 4 .2H 2 O). In the X-ray diffraction pattern, it is known that dihydrate gypsum shows a clear diffraction peak at a diffraction angle of 11 to 12 °, and hemihydrate gypsum shows a clear diffraction peak at a diffraction angle of 14 to 15 °. From this known information and powder X-ray diffraction of a coating film obtained by applying and curing a kneaded mixture of a gypsum composition and water, the hydration reaction of the hemihydrate gypsum in the gypsum composition is suppressed. It is possible to confirm whether or not it is configured so that it is preferably configured so that the initial time of the hydration reaction is later than the completion time of drying and curing.

すなわち、本実施形態の石膏組成物は、石膏組成物に水を加えて乾燥硬化させて塗膜としたときの粉末Ｘ線回折において、石膏組成物に含有されていた半水石膏の回折ピークを示し、その半水石膏の水和反応に基づく二水石膏の回折ピークを示さないことが好ましい。本明細書において、「半水石膏の水和反応に基づく二水石膏の回折ピーク」とは、前記塗膜とする前の石膏組成物に含有されている半水石膏が水和反応して生じる二水石膏の回折ピークを意味する。本発明の一実施形態の石膏組成物（及び石膏系塗材）には、例えば充填剤などの目的で二水石膏が含有されていてもよい。この場合には、その石膏組成物に水を加えて塗膜としたときの粉末Ｘ線回折において、もともと石膏組成物に含有されていた二水石膏の回折ピークが示され得る。したがって、上記の粉末Ｘ線回折による構成の確認は、二水石膏が配合されていない石膏組成物を用いた場合、又は二水石膏が配合された石膏組成物の場合にはその二水石膏が除去された石膏組成物を用いた場合に、行うことができる。以下、本発明の一実施形態の石膏組成物（石膏系塗材）の粉末Ｘ線回折における回折ピークに関しては、二水石膏を含有しない石膏組成物（二水石膏を配合していない石膏組成物や二水石膏を除いた石膏組成物など）を用いて分析される場合について述べる。なお、前記粉末Ｘ線回折の測定は、後記実施例で述べる条件で行うことができる。   That is, the gypsum composition of the present embodiment shows the diffraction peak of hemihydrate gypsum contained in the gypsum composition in powder X-ray diffraction when adding water to the gypsum composition and drying and curing to form a coating film. And preferably does not show the diffraction peak of dihydrate gypsum based on the hydration reaction of the hemihydrate gypsum. In the present specification, “diffraction peak of dihydrate gypsum based on hydration reaction of hemihydrate gypsum” means that hydrated gypsum contained in the gypsum composition before forming the coating film is hydrated. It means the diffraction peak of dihydrate gypsum. The gypsum composition (and gypsum-based coating material) of one embodiment of the present invention may contain dihydrate gypsum for the purpose of, for example, a filler. In this case, in powder X-ray diffraction when water is added to the gypsum composition to form a coating film, the diffraction peak of dihydrate gypsum originally contained in the gypsum composition can be shown. Therefore, the confirmation of the composition by the above powder X-ray diffraction can be performed by using a gypsum composition not containing dihydrate gypsum, or in the case of a gypsum composition containing dihydrate gypsum. This can be done when the removed gypsum composition is used. Hereinafter, regarding the diffraction peak in powder X-ray diffraction of the gypsum composition (gypsum coating material) of one embodiment of the present invention, a gypsum composition not containing dihydrate gypsum (gypsum composition not containing dihydrate gypsum) And gypsum composition excluding dihydrate gypsum). In addition, the measurement of the said powder X-ray diffraction can be performed on the conditions described in the postscript Example.

一方、従来の反応硬化形の石膏系塗材を薄塗りする場合のように、塗膜にドライアウトが生じる場合には、従来の石膏組成物と水との混合物を硬化させることで形成される塗膜の粉末Ｘ線回折において、半水石膏の回折ピークとその半水石膏の水和反応に基づく二水石膏の回折ピークの両方を示す。また、従来の反応硬化形の石膏系塗材を厚塗りする場合のように、ドライアウトが生じ難く、塗膜のほぼ全体に半水石膏の水和反応による二水石膏が形成されている場合には、半水石膏の回折ピークを示さず、二水石膏の回折ピークを示す。   On the other hand, when dry-out occurs in the coating film as in the case of thinly applying a conventional reaction-curable gypsum-based coating material, it is formed by curing a mixture of a conventional gypsum composition and water. In the powder X-ray diffraction of the coating film, both the diffraction peak of hemihydrate gypsum and the diffraction peak of dihydrate gypsum based on the hydration reaction of the hemihydrate gypsum are shown. In addition, when thickening a conventional reaction-curing gypsum-based coating material, it is difficult for dryout to occur, and dihydrate gypsum is formed almost entirely on the coating film by the hydration reaction of hemihydrate gypsum. Does not show the diffraction peak of hemihydrate gypsum, but shows the diffraction peak of dihydrate gypsum.

また、石膏組成物に水を加えたときの水和反応の始発時間を測定することにより、石膏組成物が、石膏組成物中の半水石膏の水和反応が抑制されるように（好ましくはその水和反応の始発時間が乾燥硬化の完了時間よりも遅くなるように）構成されているか否かを確認することも可能である。すなわち、本実施形態の石膏組成物は、石膏組成物に水を加えたときの水和反応の始発時間が２４時間以上であることが好ましい。前記水和反応の始発時間は、ＪＩＳ Ａ６９０４に記載された標準軟度を針入り深さ２０±２ｍｍとして、その他はＪＩＳ Ａ６９０４に準じ、ＪＩＳ Ａ６９０４にいう凝結の始発を本明細書においては水和反応の始発として、測定される。その水和反応の始発時間が２４時間以上（より好ましくは４８時間以上）であれば、通常用いられる量の水を石膏組成物に加えて石膏系塗材としたときに、水和反応が始まる前に石膏系塗材中の水分は被着体に吸収され、または、空気中に蒸発し、石膏系塗材は乾燥硬化による塗膜を形成しやすい。   In addition, by measuring the initial time of the hydration reaction when water is added to the gypsum composition, the gypsum composition can suppress the hydration reaction of the hemihydrate gypsum in the gypsum composition (preferably It is also possible to check whether or not the initial time of the hydration reaction is configured to be slower than the completion time of the drying and curing. That is, in the gypsum composition of the present embodiment, the initial time of the hydration reaction when water is added to the gypsum composition is preferably 24 hours or more. The initial time of the hydration reaction is the standard softness described in JIS A6904 with a needle penetration depth of 20 ± 2 mm, the other is in accordance with JIS A6904, and the initial setting of condensation in JIS A6904 is hydrated in this specification. Measured as the first reaction. If the initial time of the hydration reaction is 24 hours or more (more preferably 48 hours or more), the hydration reaction starts when a gypsum-based coating material is added to the gypsum composition with a commonly used amount of water. Moisture in the gypsum-based coating material is previously absorbed by the adherend or evaporated into the air, and the gypsum-based coating material tends to form a coating film by dry curing.

なお、ＪＩＳ Ａ６９０９の「建築用仕上塗材」における薄塗材及び厚塗材の各塗り厚に関する記載を考慮して、本明細書において、「薄塗り」とは、塗り厚が３ｍｍ程度以下（例えば０．５〜３ｍｍ）の塗布をいうものとする。また、同様に、「厚塗り」とは、塗り厚が３ｍｍ超（例えば４〜１０ｍｍ）程度の塗布をいうものとする。さらに、本明細書において、「平均粒子径」とは、レーザー回折・散乱法を利用した粒度分布測定装置を用いて測定される、体積平均径（ＭＶ）をいう。次に、本実施形態の石膏組成物中の成分ごとに、本実施形態の石膏組成物の構成についてさらに詳述する。   In consideration of the description of each coating thickness of the thin coating material and the thick coating material in the “finishing coating material for building” of JIS A6909, in this specification, “thin coating” means a coating thickness of about 3 mm or less (for example, 0 .5-3mm). Similarly, “thick coating” refers to coating having a coating thickness of more than 3 mm (for example, 4 to 10 mm). Further, in the present specification, the “average particle diameter” refers to a volume average diameter (MV) measured using a particle size distribution measuring apparatus using a laser diffraction / scattering method. Next, the configuration of the gypsum composition of the present embodiment will be described in detail for each component in the gypsum composition of the present embodiment.

半水石膏は、硫酸カルシウムの１／２水和物［ＣａＳＯ4・１／２Ｈ2Ｏ］であり、焼石膏とも称される。本明細書において、「半水石膏」には、α型半水石膏及びβ型半水石膏が含まれ、また、空気中の水分を吸収して容易に半水石膏に変化することからIII型無水石膏（ＣａＳＯ4）も含まれるものとする。半水石膏の原料石膏としては、天然物（バサニ石等）、副生石膏、及び廃石膏のいずれも用いることができる。製造コスト、リサイクル促進、環境保護等の観点から、本実施形態の石膏組成物中に含有させる半水石膏の原料石膏の一部又は全部が、廃石膏であることが好ましい。Hemihydrate gypsum is calcium sulfate hemihydrate [CaSO 4 · 1 / 2H 2 O], also called calcined gypsum. In the present specification, “hemihydrate gypsum” includes α-type hemihydrate gypsum and β-type hemihydrate gypsum, and absorbs moisture in the air and easily changes to hemihydrate gypsum. Anhydrous gypsum (CaSO 4 ) is also included. As raw gypsum for hemihydrate gypsum, any of natural products (basani stone, etc.), by-product gypsum, and waste gypsum can be used. From the viewpoint of production cost, promotion of recycling, environmental protection, and the like, it is preferable that part or all of the raw gypsum of hemihydrate gypsum contained in the gypsum composition of this embodiment is waste gypsum.

本実施形態の石膏組成物では、半水石膏として、大気中又は水中（水蒸気中を含む）で焼成して得られるα型半水石膏及びβ型半水石膏のいずれか一方又は両方を用いることが好ましく、それらの混合物を用いることも好ましい。半水石膏の平均粒子径を５０μｍ以下に調整しやすい観点から、β型半水石膏がより好ましい。なお、α型半水石膏は天然石膏等の二水石膏を、例えばオートクレーブを用いて水中又は水蒸気中で加圧焼成することにより製造できる。また、β型半水石膏は天然石膏等の二水石膏を大気中で常圧焼成することにより製造できる。   In the gypsum composition of the present embodiment, one or both of α-type hemihydrate gypsum and β-type hemihydrate gypsum obtained by firing in the air or water (including in water vapor) is used as the hemihydrate gypsum. It is preferable to use a mixture thereof. From the viewpoint of easily adjusting the average particle size of hemihydrate gypsum to 50 μm or less, β-type hemihydrate gypsum is more preferable. The α-type hemihydrate gypsum can be produced by subjecting dihydrate gypsum such as natural gypsum to pressure firing in water or steam using, for example, an autoclave. Β-type hemihydrate gypsum can be produced by firing dihydrate gypsum such as natural gypsum at atmospheric pressure.

本実施形態の石膏組成物に水を加えた石膏系塗材を用いて平滑な塗膜を形成するために、石膏組成物には、平均粒子径が５０μｍ以下の半水石膏を用いる。平均粒子径が５０μｍよりも大きい半水石膏を用いると、石膏組成物に水を加えた石膏系塗材を乾燥硬化させたことによる塗膜の表面が粗くなるとともに、表面硬度が低くなってしまい、傷つきやすい面となる場合がある。   In order to form a smooth coating film using a gypsum-based coating material obtained by adding water to the gypsum composition of this embodiment, hemihydrate gypsum having an average particle size of 50 μm or less is used for the gypsum composition. When hemihydrate gypsum having an average particle size larger than 50 μm is used, the surface of the coating film is roughened and the surface hardness is lowered by drying and curing the gypsum coating material obtained by adding water to the gypsum composition. In some cases, the surface may be easily damaged.

より平滑な塗膜を形成する観点から、半水石膏の平均粒子径は、４０μｍ以下であることがより好ましく、３０μｍ以下であることがさらに好ましい。半水石膏の平均粒子径の下限は特に制限されないが、粉砕設備及びコストの観点から、半水石膏の平均粒子径は、１μｍ以上であることが好ましく、１０μｍ以上であることがより好ましい。   From the viewpoint of forming a smoother coating film, the average particle size of hemihydrate gypsum is more preferably 40 μm or less, and further preferably 30 μm or less. The lower limit of the average particle size of the hemihydrate gypsum is not particularly limited, but from the viewpoint of grinding equipment and cost, the average particle size of the hemihydrate gypsum is preferably 1 μm or more, and more preferably 10 μm or more.

本実施形態の石膏組成物に水を加えた石膏系塗材を用いて平滑な塗膜を形成するために、石膏組成物には、平均粒子径が５０μｍ以下の炭酸カルシウムを用いる。平均粒子径が５０μｍよりも大きい炭酸カルシウムを用いると、石膏系塗材を乾燥硬化させたことによる塗膜の表面が粗くなるとともに、表面硬度が低くなってしまい、傷つきやすい面となる場合がある。石膏組成物に含有させる炭酸カルシウム及び前述の半水石膏の平均粒子径がいずれも５０μｍ以下であることにより、石膏系塗材を薄塗りする場合でも、平滑かつ表面硬度の高い塗膜を形成することが可能となる。   In order to form a smooth coating film using a gypsum-based coating material obtained by adding water to the gypsum composition of the present embodiment, calcium carbonate having an average particle diameter of 50 μm or less is used for the gypsum composition. When calcium carbonate having an average particle diameter larger than 50 μm is used, the surface of the coating film is roughened by drying and curing the gypsum-based coating material, and the surface hardness is lowered, which may be easily damaged. . When the average particle size of calcium carbonate and hemihydrate gypsum contained in the gypsum composition is 50 μm or less, a smooth and high surface hardness coating film is formed even when the gypsum coating material is thinly coated. It becomes possible.

より平滑な塗膜を形成する観点から、炭酸カルシウムの平均粒子径は、４０μｍ以下であることがより好ましく、３０μｍ以下であることがさらに好ましい。炭酸カルシウムの平均粒子径の下限は特に制限されないが、粉砕設備及びコストの観点から、０．１μｍ以上であることが好ましく、１μｍ以上であることがより好ましく、１０μｍ以上であることがさらに好ましい。   From the viewpoint of forming a smoother coating film, the average particle size of calcium carbonate is more preferably 40 μm or less, and further preferably 30 μm or less. The lower limit of the average particle diameter of calcium carbonate is not particularly limited, but is preferably 0.1 μm or more, more preferably 1 μm or more, and further preferably 10 μm or more from the viewpoint of grinding equipment and cost.

石膏組成物中の炭酸カルシウムの含有量は、半水石膏１００質量部に対して、１０〜４００質量部である。半水石膏１００質量部に対して、炭酸カルシウムの含有量が１０質量部未満であると、その石膏組成物に水を加えた石膏系塗材の乾燥硬化によって形成される塗膜の表面が粗くなりやすい。これは、炭酸カルシウムの含有量に対して半水石膏の含有量が多くなり過ぎることで、その石膏組成物に水を加えた石膏系塗材を被着体に鏝塗りする際に粘り気が生じ、鏝切れし難くなることが原因と考えられる。   The content of calcium carbonate in the gypsum composition is 10 to 400 parts by mass with respect to 100 parts by mass of hemihydrate gypsum. When the content of calcium carbonate is less than 10 parts by mass with respect to 100 parts by mass of hemihydrate gypsum, the surface of the coating film formed by dry curing of the gypsum-based coating material obtained by adding water to the gypsum composition is rough. Prone. This is because the content of hemihydrate gypsum becomes too much relative to the content of calcium carbonate, and stickiness is generated when the gypsum composition with water added to the gypsum composition is applied to the adherend. This is thought to be caused by difficulty in cutting.

一方、半水石膏１００質量部に対して、炭酸カルシウムの含有量が４００質量部を超えると、その石膏組成物に水を加えた石膏系塗材の乾燥硬化によって形成される塗膜の表面が粗くなるとともに、表面硬度が低く、傷つきやすい塗膜となる場合がある。これは、炭酸カルシウムの含有量が４００質量部を超える石膏組成物に水を加えた石膏系塗材を被着体に鏝塗りすると、石膏系塗材の乾燥硬化により塗膜が形成される過程でその表面側がより硬くなりやすく、固まり方に偏りが生じ、鏝塗りした際の鏝波が鏝押さえ作業によっても消え難いことが原因と考えられる。   On the other hand, when the content of calcium carbonate exceeds 400 parts by mass with respect to 100 parts by mass of hemihydrate gypsum, the surface of the coating film formed by the dry curing of the gypsum-based coating material in which water is added to the gypsum composition. In addition to becoming rough, the surface hardness may be low and the coating film may be easily damaged. This is a process in which a coating film is formed by dry-curing a gypsum-based coating material when a gypsum-based coating material in which water is added to a gypsum composition having a calcium carbonate content exceeding 400 parts by mass is applied to the adherend. This is probably because the surface side tends to become harder, the setting method is biased, and the tsunami waves are not easily erased by the heel pressing work.

本実施形態の石膏組成物では、平滑かつ表面硬度の高い塗膜を得る観点から、炭酸カルシウムの含有量は、半水石膏１００質量部に対して、１０〜３００質量部であることが好ましく、１０〜２００質量部であることがより好ましい。   In the gypsum composition of this embodiment, from the viewpoint of obtaining a smooth and high surface hardness coating film, the content of calcium carbonate is preferably 10 to 300 parts by mass with respect to 100 parts by mass of hemihydrate gypsum, More preferably, it is 10-200 mass parts.

本実施形態の石膏組成物には、半水石膏の水和反応を抑制するために、凝結遅延剤を石膏系塗材の水和反応の始発時間よりも乾燥硬化の完了時間が早くなる量で含有させる。例えば凝結遅延剤としてタンパク質分解物を用いた場合、石膏組成物中、半水石膏１００質量部に対して、凝結遅延剤を０．１質量部以上の割合にて含有させる。半水石膏１００質量部に対して、凝結遅延剤の含有量が０．１質量部未満であると、半水石膏の一部に水和反応が生じる可能性がある。その結果、この場合、その石膏組成物に水を加えた石膏系塗材の硬化によって形成される塗膜において、半水石膏の部分的又は不均一な水和反応に起因した色ムラが発生する可能性がある。   In the gypsum composition of the present embodiment, in order to suppress the hydration reaction of hemihydrate gypsum, the setting retarder is added in such an amount that the completion time of drying and curing is earlier than the initial time of the hydration reaction of the gypsum-based coating material. Contain. For example, when a proteolysate is used as a setting retarder, the setting retarder is contained in a proportion of 0.1 parts by mass or more with respect to 100 parts by mass of hemihydrate gypsum in the gypsum composition. If the content of the setting retarder is less than 0.1 parts by mass with respect to 100 parts by mass of hemihydrate gypsum, a hydration reaction may occur in part of the hemihydrate gypsum. As a result, in this case, in the coating film formed by curing the gypsum-based coating material obtained by adding water to the gypsum composition, color unevenness due to partial or non-uniform hydration reaction of hemihydrate gypsum occurs. there is a possibility.

凝結遅延剤の含有量の上限は特に限定されないが、凝結遅延剤は半水石膏の水和反応を抑制可能である量であれば足り、その量があまりに多いとコストが上昇する原因となるとともに、凝結遅延剤自体に色がある場合には塗膜が一部変色する可能性がある。これらの観点から、凝結遅延剤の含有量は、半水石膏１００質量部に対して、１５質量部以下であることが好ましく、１０質量部以下であることがより好ましく、２質量部以下であることがさらに好ましい。したがって、石膏組成物中の凝結遅延剤の含有量は、半水石膏１００質量部に対して、好ましくは０．１〜１５質量部、より好ましくは０．１〜１０質量部、さらに好ましくは０．１〜２質量部である。半水石膏の水和反応をより抑制しやすくする観点から、石膏組成物中の凝結遅延剤の含有量は、半水石膏１００質量部に対して、０．２質量部以上であることがより好ましい。   The upper limit of the content of the setting retarder is not particularly limited, but it is sufficient that the setting retarder is capable of suppressing the hydration reaction of hemihydrate gypsum, and if the amount is too large, the cost increases. When the setting retarder itself has a color, the coating film may be partially discolored. From these viewpoints, the content of the setting retarder is preferably 15 parts by mass or less, more preferably 10 parts by mass or less, with respect to 100 parts by mass of hemihydrate gypsum, and 2 parts by mass or less. More preferably. Therefore, the content of the setting retarder in the gypsum composition is preferably 0.1 to 15 parts by mass, more preferably 0.1 to 10 parts by mass, and still more preferably 0 to 100 parts by mass of hemihydrate gypsum. .1 to 2 parts by mass. From the viewpoint of easily suppressing the hydration reaction of hemihydrate gypsum, the content of the setting retarder in the gypsum composition is more than 0.2 parts by mass with respect to 100 parts by mass of hemihydrate gypsum. preferable.

なお、凝結遅延剤の平均粒子径は特に限定されないが、凝結遅延剤のなかでも小さい粒径を持つものが好ましく、具体的には、５０μｍ以下であることが好ましく、半水石膏及び炭酸カルシウムの平均粒子径以下であることがより好ましい。   The average particle diameter of the setting retarder is not particularly limited, but among the setting retarders, those having a small particle diameter are preferable, and specifically, 50 μm or less is preferable. More preferably, the average particle size is equal to or smaller than the average particle size.

凝結遅延剤としては、クエン酸、コハク酸、酢酸、リンゴ酸、エチレンジアミン四酢酸、ジエチレントリアミン五酢酸、及びこれらの塩、並びにショ糖、澱粉、及びタンパク質分解物からなる群より選択される少なくとも１種を用いることができる。クエン酸塩、コハク酸塩、酢酸塩、リンゴ酸塩、エチレンジアミン四酢酸塩、及びジエチレントリアミン五酢酸塩における塩を構成するイオンとしては、ナトリウム、カリウム、リチウム、カルシウム、及びマグネシウムなどの金属イオン、並びに有機アンモニウムイオンなどを挙げることができる。前記タンパク質分解物としては、動物及び／又は植物由来のタンパク質を、塩酸などで加水分解して得られたものやプロテアーゼなどの酵素で分解して得られたものなどを用いることができる。例えば、ペプトン、ゼラチン、ケラチン、カゼイン、カゼインカルシウム、卵アルブミン、γ-グロブリン、又はこれらの混合物などのタンパク質分解物を使用することができる。そのような凝結遅延剤の市販品としては、例えば、ＳＩＣＩＴ社製の商品名「ＰＬＡＳＴ ＲＥＴＡＲＤ ＰＥ」などが挙げられる。   The setting retarder is at least one selected from the group consisting of citric acid, succinic acid, acetic acid, malic acid, ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, and salts thereof, and sucrose, starch, and protein degradation products. Can be used. The ions constituting the salts in citrate, succinate, acetate, malate, ethylenediaminetetraacetate, and diethylenetriaminepentaacetate include metal ions such as sodium, potassium, lithium, calcium, and magnesium, and Examples include organic ammonium ions. Examples of the proteolysate include those obtained by hydrolyzing animal and / or plant-derived proteins with hydrochloric acid or the like, or those obtained by decomposing with an enzyme such as protease. For example, proteolytic products such as peptone, gelatin, keratin, casein, calcium caseinate, ovalbumin, γ-globulin, or mixtures thereof can be used. As a commercial item of such a set retarder, for example, trade name “PLAST RETALD PE” manufactured by SICIT, and the like can be mentioned.

ここで、従来の石膏系塗材は、半水石膏を用い、水を加えることで半水石膏の水和反応を生じさせ、半水石膏が二水石膏へと相変化して硬化する反応硬化形の塗材として用いられてきた。こうした従来の反応硬化形の石膏系塗材では、被着体への塗布前の段階で、半水石膏が水和反応しないように、仮に凝結遅延剤を用いることがあっても、塗布後に半水石膏を水和反応させるために、凝結促進剤などの水和反応を促進させる添加剤を配合する必要がある。これに対して、本実施形態の石膏組成物は、半水石膏の水和反応が抑制されるように構成され、乾燥硬化形の石膏系塗材に用いられる。そのため、本発明の一実施形態の石膏組成物は、凝結促進剤を実質的に含有しないことが好ましい。凝結促進剤を実質的に含有しない石膏組成物は、その石膏組成物と水との混合物から形成される塗膜の粉末Ｘ線回折において、半水石膏の水和反応に基づく二水石膏の明らかな回折ピークを有しないことで確認される。   Here, the conventional gypsum-based coating material uses hemihydrate gypsum, and when water is added, it causes a hydration reaction of the hemihydrate gypsum, and the reaction curing in which the hemihydrate gypsum changes into dihydrate gypsum and cures. It has been used as a form coating material. In such a conventional reaction-curing gypsum-based coating material, even if a setting retarder is used to prevent hydration of the hemihydrate gypsum before application to the adherend, In order to hydrate the water gypsum, it is necessary to add an additive that accelerates the hydration reaction such as a setting accelerator. In contrast, the gypsum composition of the present embodiment is configured so that the hydration reaction of hemihydrate gypsum is suppressed, and is used for a dry-cured gypsum-based coating material. Therefore, it is preferable that the gypsum composition of one embodiment of the present invention does not substantially contain a setting accelerator. A gypsum composition that is substantially free of setting accelerator is a dihydrate gypsum based on the hydration reaction of hemihydrate gypsum in powder X-ray diffraction of a coating formed from a mixture of the gypsum composition and water. This is confirmed by having no diffractive peak.

本実施形態の石膏組成物は、前述の半水石膏及び炭酸カルシウムを主成分とする組成物であることが好ましい。具体的には、石膏組成物中の半水石膏及び炭酸カルシウムの合計の含有割合（質量％）は、石膏組成物の固形分の全質量を基準として、５０質量％以上であることが好ましく、より好ましくは６０質量％以上、さらに好ましくは７０質量％以上である。また、石膏組成物の固形分の全質量を基準とした石膏組成物中の半水石膏、炭酸カルシウム、及び凝結遅延剤の各含有割合（質量％）は、それぞれ前述した含有量（質量部）の関係を前提として、次のような範囲内にすることができる。すなわち、石膏組成物の固形分中、半水石膏の含有割合は１８〜９０質量％の範囲内であることが好ましく、より好ましくは２０〜９０質量％の範囲内である。石膏組成物の固形分中、炭酸カルシウムの含有割合は８〜８０質量％の範囲内であることが好ましく、より好ましくは８〜７０質量％の範囲内であり、凝結遅延剤の含有割合は０．０２〜８質量％の範囲内であることが好ましい。   The gypsum composition of the present embodiment is preferably a composition mainly composed of the above-mentioned hemihydrate gypsum and calcium carbonate. Specifically, the total content (mass%) of hemihydrate gypsum and calcium carbonate in the gypsum composition is preferably 50% by mass or more based on the total mass of the solid content of the gypsum composition, More preferably, it is 60 mass% or more, More preferably, it is 70 mass% or more. Moreover, each content rate (mass%) of hemihydrate gypsum, calcium carbonate, and a setting retarder in the gypsum composition based on the total mass of the solid content of the gypsum composition is the content (parts by mass) described above. Assuming this relationship, it can be within the following range. That is, in the solid content of the gypsum composition, the content ratio of hemihydrate gypsum is preferably in the range of 18 to 90% by mass, and more preferably in the range of 20 to 90% by mass. In the solid content of the gypsum composition, the content of calcium carbonate is preferably in the range of 8 to 80% by mass, more preferably in the range of 8 to 70% by mass, and the content of the setting retarder is 0. It is preferable to be within the range of 0.02 to 8% by mass.

本実施形態の石膏組成物には、本発明の目的を阻害しない範囲において、上記成分以外にも種々の添加剤を含有させることができる。添加剤としては、例えば、糊剤、着色剤、増粘剤、消泡剤、凝結促進剤、充填剤、骨材、軽量化材、減水剤、撥水剤、撥水助剤、ホルムアルデヒドキャッチャー剤、起泡剤、不凍剤、防カビ剤、防錆剤、防腐剤、抗菌剤、殺菌剤、粘度調整剤、可塑剤、潤沢剤、滑り剤、ｐＨ調整剤、及び吸放湿性材料などを挙げることができる。   The gypsum composition of the present embodiment can contain various additives in addition to the above components as long as the object of the present invention is not impaired. Examples of additives include pastes, colorants, thickeners, antifoaming agents, setting accelerators, fillers, aggregates, lightening materials, water reducing agents, water repellents, water repellent aids, and formaldehyde catchers. Foaming agent, antifreeze agent, antifungal agent, rust preventive agent, antiseptic agent, antibacterial agent, bactericidal agent, viscosity modifier, plasticizer, lubricant, slip agent, pH adjuster, hygroscopic material, etc. Can be mentioned.

本実施形態の石膏組成物には、糊剤を含有させることが好ましい。石膏組成物が糊剤を含有することで、その石膏組成物に水を加えて調製した石膏系塗材を被着体に塗布し、乾燥硬化させて塗膜を形成したときに、塗膜の締まりや被着体に対する付着性を向上させ、平滑性や表面硬度を高めることが可能となる。   The gypsum composition of this embodiment preferably contains a paste. When the gypsum composition contains a paste, a gypsum coating material prepared by adding water to the gypsum composition is applied to an adherend and dried and cured to form a coating film. It is possible to improve the tightness and adherence to the adherend, and increase the smoothness and surface hardness.

糊剤としては、例えば、ポリビニルアルコール、エチレン−酢酸ビニル（ＥＶＡ）コポリマー、エチレン−バーサチック酸ビニルコポリマー及び酢酸ビニル−バーサチック酸ビニルコポリマーなどのビニルエステルとエチレンモノマーとのコポリマー、ポリアクリル酸、酢酸ビニル−アクリルコポリマー、スチレン−アクリルコポリマー、スチレン−ブタジエンコポリマー、酢酸ビニル−バーサチック酸ビニル−アクリルターポリマー、酢酸ビニル−バーサチック酸ビニル−マレイン酸ビニルターポリマー、及びアクリルターポリマーなどを挙げることができる。これらの１種又は２種以上を用いることができる。糊剤としては、ポリビニルアルコール、アクリル系樹脂、酢酸ビニル系樹脂が好ましい。石膏組成物中の糊剤の含有量は、石膏組成物の全質量を基準として、１〜１０質量％であることが好ましい。   Examples of the sizing agent include copolymers of vinyl esters and ethylene monomers such as polyvinyl alcohol, ethylene-vinyl acetate (EVA) copolymer, ethylene-vinyl versatate copolymer and vinyl acetate-vinyl versatate copolymer, polyacrylic acid, vinyl acetate. -Acrylic copolymers, styrene-acrylic copolymers, styrene-butadiene copolymers, vinyl acetate-vinyl versatic acid-acrylic terpolymers, vinyl acetate-vinyl versatic acid-vinyl maleate terpolymers, acrylic terpolymers and the like. These 1 type (s) or 2 or more types can be used. As the paste, polyvinyl alcohol, acrylic resin, and vinyl acetate resin are preferable. It is preferable that content of the paste in a gypsum composition is 1-10 mass% on the basis of the total mass of a gypsum composition.

半水石膏や炭酸カルシウムは白色であるため、本実施形態の石膏組成物を用いて調製される石膏系塗材から、漆喰のような白色の塗膜を形成することができ、例えば、漆喰のような白色の壁面を形成することができる。その一方で、塗膜を白色以外の色にしたい場合には、石膏組成物に着色剤を含有させることができる。着色剤としては主に染料と顔料の２種類があるが、顔料を用いることが好ましい。   Since hemihydrate gypsum and calcium carbonate are white, a white coating film such as plaster can be formed from a gypsum-based coating material prepared using the gypsum composition of the present embodiment. Such a white wall surface can be formed. On the other hand, when it is desired to make the coating film have a color other than white, a colorant can be contained in the gypsum composition. Although there are mainly two types of colorants, dyes and pigments, it is preferable to use pigments.

顔料としては、種々の色彩を有する無機顔料及び有機顔料を用いることができる。無機顔料としては、特に限定されないが、例えば、酸化亜鉛、酸化鉄、二酸化チタン、酸化クロム、水酸化アルミニウム、黄色酸化鉄、黄鉛、ジンククロメート、タルク、群青、鉛白、カーボンブラック、及びリン酸塩などを挙げることができる。また、有機顔料としては、特に限定されないが、例えば、アゾ系顔料、ニトロ系顔料、ニトロソ系顔料、フタロシアニン顔料、及び縮合多環顔料などを挙げることができる。また、レーキ顔料も使用することができる。石膏組成物中の顔料の含有量は、所望の色彩（明度、色度、彩度）によって適宜設定することができる。   As the pigment, inorganic pigments and organic pigments having various colors can be used. Examples of inorganic pigments include, but are not limited to, zinc oxide, iron oxide, titanium dioxide, chromium oxide, aluminum hydroxide, yellow iron oxide, yellow lead, zinc chromate, talc, ultramarine blue, lead white, carbon black, and phosphorus. Examples thereof include acid salts. The organic pigment is not particularly limited, and examples thereof include azo pigments, nitro pigments, nitroso pigments, phthalocyanine pigments, and condensed polycyclic pigments. Lake pigments can also be used. The content of the pigment in the gypsum composition can be appropriately set depending on the desired color (lightness, chromaticity, saturation).

本実施形態の石膏組成物には、石膏系塗材のチキソトロピーを向上させることを目的として、増粘剤を含有させることができる。増粘剤としては、例えば、セルロース系増粘剤、ポリアクリルアミド類、α化澱粉、デンプン誘導体類、アタパルガイト、海泡石、モンモリロナイト、及びベントナイトなどの粘土類などを挙げることができる。その中でもセルロース系増粘剤が好ましい。セルロース系増粘剤の好適な具体例としては、ヒドロキシエチルセルロース、エチルヒドロキシエチルセルロース、メチルヒドロキシプロピルセルロース、メチルヒドロキシエチルセルロース、ヒドロキシプロピルメチルセルロース、メチルセルロース、及びカルボキシメチルセルロース、並びにこれらの塩などを挙げることができる。これらのセルロース系増粘剤のうちの１種又は２種以上を用いることができる。石膏組成物中の増粘剤の含有量は、石膏組成物の全質量を基準として、０．０１〜２質量％であることが好ましい。   The gypsum composition of the present embodiment can contain a thickener for the purpose of improving the thixotropy of the gypsum-based coating material. Examples of the thickener include cellulosic thickeners, polyacrylamides, pregelatinized starch, starch derivatives, attapulgite, leptite, montmorillonite, and clays such as bentonite. Among these, a cellulose thickener is preferable. Specific examples of suitable cellulose-based thickeners include hydroxyethyl cellulose, ethyl hydroxyethyl cellulose, methyl hydroxypropyl cellulose, methyl hydroxyethyl cellulose, hydroxypropyl methyl cellulose, methyl cellulose, carboxymethyl cellulose, and salts thereof. One or more of these cellulosic thickeners can be used. The content of the thickener in the gypsum composition is preferably 0.01 to 2% by mass based on the total mass of the gypsum composition.

本実施形態の石膏組成物には、石膏系塗材を被着体に塗布する際に鏝塗りによる筋引きを防止し、平滑性を高めることを目的として、消泡剤を含有させることができる。消泡剤としては、例えば、シリコーン系、アルコール系、及びポリエーテル系の各消泡剤を用いることができ、１種単独で又は２種以上を組み合わせて用いることができる。これらの消泡剤は、合成物質又は植物由来の天然物質など、公知のものを用いることができる。石膏組成物中の消泡剤の含有量は、石膏組成物の全質量を基準として、０．０１〜１質量％であることが好ましい。   The gypsum composition of the present embodiment can contain an antifoaming agent for the purpose of preventing streaking due to wrinkling and enhancing smoothness when a gypsum-based coating material is applied to an adherend. . As the antifoaming agent, for example, silicone-based, alcohol-based, and polyether-based antifoaming agents can be used, and one type can be used alone, or two or more types can be used in combination. As these antifoaming agents, known substances such as synthetic substances or plant-derived natural substances can be used. The content of the antifoaming agent in the gypsum composition is preferably 0.01 to 1% by mass based on the total mass of the gypsum composition.

本実施形態の石膏組成物は、例えば、粉末状、錠剤状、及び塊状などの形態とすることができる。石膏組成物に含有される半水石膏、炭酸カルシウム、及び凝結遅延剤などの各成分を、まとめて単一の混合形態として使用してもよく、単一の剤の形態として使用してもよく、別々にしてセット（キット）として使用してもよい。   The gypsum composition of this embodiment can be in the form of, for example, a powder, a tablet, or a lump. Each component such as hemihydrate gypsum, calcium carbonate, and setting retarder contained in the gypsum composition may be used together as a single mixed form or may be used as a single agent form These may be used separately as a set (kit).

上記の各形態のうち、石膏組成物は、粉末状の形態（粉末の集合体）であることが好ましい。石膏組成物が粉末状の形態である場合、被着体に塗材を塗布する現場において、石膏組成物に水を加えることで容易にスラリー状（液状）の石膏系塗材を調製することが可能となる。石膏組成物を粉末状の形態としておき、被着体に塗布する際、好ましくは被着体に塗布する直前に、石膏組成物に水を添加して石膏系塗材を調製して使用すれば、石膏組成物中の半水石膏の水和反応をより防止し易くなる。そのため、塗材の硬化による塗膜の色ムラをより抑制しやすくなる。   Among the above forms, the gypsum composition is preferably in a powder form (a powder aggregate). When the gypsum composition is in a powder form, a slurry (liquid) gypsum coating material can be easily prepared by adding water to the gypsum composition at the site where the coating material is applied to the adherend. It becomes possible. When the gypsum composition is put into a powder form and applied to the adherend, preferably immediately before application to the adherend, water is added to the gypsum composition to prepare and use a gypsum-based coating material. It becomes easier to prevent the hydration reaction of hemihydrate gypsum in the gypsum composition. Therefore, it becomes easier to suppress color unevenness of the coating film due to curing of the coating material.

＜石膏系塗材＞
本明細書において、水を含有する石膏組成物を石膏系塗材と称することとする。すなわち、本発明の一実施形態の石膏系塗材は、平均粒子径が５０μｍ以下の半水石膏と、平均粒子径が５０μｍ以下の炭酸カルシウムと、凝結遅延剤と、水と、を含有する。そして、この石膏系塗材では、半水石膏１００質量部に対して、炭酸カルシウムの含有量が１０〜４００質量部であり、凝結遅延剤の含有量が０．１質量部以上である。<Gypsum coating material>
In the present specification, a gypsum composition containing water is referred to as a gypsum-based coating material. That is, the gypsum-based coating material of one embodiment of the present invention contains hemihydrate gypsum having an average particle diameter of 50 μm or less, calcium carbonate having an average particle diameter of 50 μm or less, a setting retarder, and water. And in this gypsum-type coating material, content of calcium carbonate is 10-400 mass parts with respect to 100 mass parts of hemihydrate gypsum, and content of a setting retarder is 0.1 mass part or more.

本実施形態の石膏系塗材は、スラリー状（液状）、ペースト状、及びジェル状などの形態とすることができる。このなかでも、石膏系塗材をそのまま被着体に塗布できるよう、石膏系塗材はスラリー状（液状）の形態であることが好ましい。水を含有する石膏系塗材として流通される場合、使用前の段階で半水石膏の水和反応を抑制するために、石膏系塗材に反応停止剤を含有させておくことが好ましい。   The gypsum-based coating material of the present embodiment can be in the form of a slurry (liquid), a paste, or a gel. Among these, the gypsum-based coating material is preferably in the form of a slurry (liquid) so that the gypsum-based coating material can be directly applied to the adherend. When it is distributed as a gypsum-based coating material containing water, it is preferable to contain a reaction terminator in the gypsum-based coating material in order to suppress the hydration reaction of hemihydrate gypsum before use.

上述のように、塗材の使用前の段階で予め水と反応停止剤とを含有させた、いわゆるレディーミクストタイプの石膏系塗材を用いることは、被着体に塗材を塗布する現場において、石膏組成物に水を添加する作業を省くことが可能となる利点を有する。なお、レディーミクストタイプの石膏系塗材には、使用の際に必要に応じて反応開始剤を添加することもできる。また、レディーミクストタイプの石膏系塗材は水を含有するため、時間の経過によって、塗材を塗布する前から一部の半水石膏が水和反応する可能性や、保管中に石膏組成物の性状が変化するなどして塗布した際に部分的に水和反応する可能性がある。このため、本発明の一実施形態の石膏組成物は、前述の粉末状の形態であることがより好ましい。   As described above, the use of a so-called ready-mixed gypsum-based coating material that contains water and a reaction stopper in advance before the coating material is used in the field where the coating material is applied to the adherend. In addition, there is an advantage that the work of adding water to the gypsum composition can be omitted. In addition, a reaction initiator can be added to the ready-mixed gypsum-based coating material as necessary at the time of use. In addition, since ready-mixed gypsum-based coating materials contain water, some hemihydrate gypsum may hydrate before the coating material is applied over time, and the gypsum composition during storage There is a possibility that a partial hydration reaction may occur when the coating is applied due to a change in the properties of. For this reason, it is more preferable that the gypsum composition of one Embodiment of this invention is the above-mentioned powdery form.

石膏系塗材における水の含有量は特に限定されず、用途に応じて、適宜決定することができる。例えば、石膏系塗材は、半水石膏、炭酸カルシウム、及び凝結遅延剤の合計１００質量部に対して、水を３０〜６０質量部含有することが好ましい。また、固形分の石膏組成物に対して、混水率が３０〜６０質量％であることが好ましい。石膏系塗材のｐＨは７以上９未満（中性付近）であることが好ましく、７以上８以下であることがより好ましく、７以上８未満（中性）であることがさらに好ましい。本明細書において、塗材のｐＨは２５℃で測定される値をいう。石膏系塗材のｐＨを調整する際にはｐＨ調整剤を適宜添加することができる。ｐＨ調整剤としては、例えば、塩酸及び硫酸等の酸、並びに水酸化ナトリウム、水酸化カリウム、及び水酸化カルシウム等の塩基を用いることができる。   The water content in the gypsum-based coating material is not particularly limited, and can be appropriately determined according to the use. For example, the gypsum-based coating material preferably contains 30 to 60 parts by mass of water with respect to a total of 100 parts by mass of hemihydrate gypsum, calcium carbonate, and a setting retarder. Moreover, it is preferable that a water mixing rate is 30-60 mass% with respect to the gypsum composition of solid content. The pH of the gypsum-based coating material is preferably 7 or more and less than 9 (near neutral), more preferably 7 or more and 8 or less, and even more preferably 7 or more and less than 8 (neutral). In this specification, pH of a coating material means the value measured at 25 degreeC. When adjusting the pH of the gypsum-based coating material, a pH adjuster can be appropriately added. As the pH adjuster, for example, acids such as hydrochloric acid and sulfuric acid, and bases such as sodium hydroxide, potassium hydroxide, and calcium hydroxide can be used.

本実施形態の石膏系塗材は、前述の石膏組成物を用いることから、半水石膏の水和反応が抑制された塗膜を形成することができ、具体的には、半水石膏の状態（硫酸カルシウムの水和数）がほぼ維持された塗膜を形成することも可能である。したがって、前記石膏系塗材によって、半水石膏の部分的又は不均一な水和反応に起因した色ムラが抑制された塗膜を形成することができる。色ムラ抑制の観点から、本実施形態の石膏系塗材は、乾燥硬化させて塗膜としたときの粉末Ｘ線回折測定において、石膏系塗材に含有されていた半水石膏の回折ピークを示し、その半水石膏の水和反応に基づく二水石膏の回折ピークを示さないことが好ましい。また、本実施形態の石膏系塗材は、前述したＪＩＳ Ａ６９０４に準じて測定される水和反応の始発時間が２４時間以上であることも好ましい。   Since the gypsum-based coating material of the present embodiment uses the above-described gypsum composition, it can form a coating film in which the hydration reaction of hemihydrate gypsum is suppressed, specifically, the state of hemihydrate gypsum It is also possible to form a coating film in which (the hydration number of calcium sulfate) is substantially maintained. Therefore, the gypsum-based coating material can form a coating film in which color unevenness due to partial or non-uniform hydration reaction of hemihydrate gypsum is suppressed. From the viewpoint of suppressing color unevenness, the gypsum coating material of the present embodiment shows the diffraction peak of hemihydrate gypsum contained in the gypsum coating material in the powder X-ray diffraction measurement when dried and cured to form a coating film. And preferably does not show the diffraction peak of dihydrate gypsum based on the hydration reaction of the hemihydrate gypsum. Moreover, it is also preferable that the initial time of the hydration reaction measured according to the above-mentioned JIS A6904 is 24 hours or more in the gypsum-based coating material of this embodiment.

石膏系塗材に含有される半水石膏及び炭酸カルシウムはともに平均粒子径が５０μｍ以下であるため、薄く平滑な塗膜を形成することが可能となる。具体的には、その石膏系塗材により、表面粗さとして、ＪＩＳ Ｂ０６０１：１９８２（ＪＩＳ Ｂ０６０１：２０１３の付属書ＪＡ）で規定される十点平均粗さＲｚ（μｍ）が、５μｍ以下、好ましくは３μｍ以下、より好ましくは２μｍ以下、さらに好ましくは１μｍ以下である塗膜を形成することが可能である。Ｒｚの値は低いほど塗膜表面が平滑であることを表す。Ｒｚの下限は特に限定されず、０．１μｍ以上とすることができる。   Since both the hemihydrate gypsum and calcium carbonate contained in the gypsum-based coating material have an average particle diameter of 50 μm or less, a thin and smooth coating film can be formed. Specifically, the ten-point average roughness Rz (μm) defined by JIS B0601: 1982 (JIS B0601: 2013 appendix JA) is preferably 5 μm or less as the surface roughness due to the gypsum-based coating material. Can form a coating film of 3 μm or less, more preferably 2 μm or less, and even more preferably 1 μm or less. The lower the value of Rz, the smoother the coating surface. The lower limit of Rz is not particularly limited, and can be 0.1 μm or more.

また、本実施形態の石膏系塗材は、ＪＩＳ Ｋ６２５３−３：２０１２に規定されるタイプＤデュロメータ硬さが５１以上、より好ましくは５６以上である塗膜を形成することが可能である。上述の表面粗さ及びタイプＤデュロメータ硬さの各値は、本実施形態の石膏系塗材を石膏ボード上に塗布し、乾燥させて硬化させた塗膜から測定される値を採ることができる。   Further, the gypsum-based coating material of the present embodiment can form a coating film having a type D durometer hardness of 51 or more, more preferably 56 or more, as defined in JIS K6253-3: 2012. Each value of the above-mentioned surface roughness and type D durometer hardness can take the value measured from the coating film which apply | coated the gypsum-type coating material of this embodiment on the gypsum board, and was dried and hardened. .

一般的に、石膏系塗材の用途としては、目地処理材や塗り壁材（下塗り用、上塗り用、及びそれら双方兼用）がある。本実施形態の乾燥硬化形の塗材用石膏組成物及び石膏系塗材は、石膏系塗材中に含有される半水石膏の水和反応を生じさせないように構成されているため、半水石膏の部分的又は不均一な水和反応に起因した色ムラを防止することが可能である。そのため、本実施形態の石膏組成物及び石膏系塗材は、表面に表れる材料や薄く形成される材料として用いられることに適しており、この観点から、塗り壁材に用いられることが好ましい。特に、本実施形態の石膏組成物及び石膏系塗材は、薄く平滑な塗膜を形成可能であることから、上塗り用、又は下塗り用及び上塗り用の双方兼用の塗り壁材に用いられることがより好ましく、塗厚が３ｍｍ以下の薄い厚さの上塗り用又は双方兼用の塗り壁材に用いられることがさらに好ましい。   In general, gypsum-based coating materials include joint treatment materials and painted wall materials (for undercoating, overcoating, and both). Since the dry-curing gypsum composition and gypsum-based coating material of the present embodiment are configured not to cause a hydration reaction of hemihydrate gypsum contained in the gypsum-based coating material, It is possible to prevent color unevenness due to partial or non-uniform hydration reaction of gypsum. Therefore, the gypsum composition and the gypsum-based coating material of this embodiment are suitable for being used as a material that appears on the surface or a material that is thinly formed. From this point of view, it is preferably used as a coating wall material. In particular, since the gypsum composition and the gypsum-based coating material of the present embodiment can form a thin and smooth coating film, the gypsum composition and the gypsum-based coating material can be used as a coating wall material for top coating or for both undercoating and top coating. More preferably, it is more preferably used for a coating wall material having a thin coating thickness of 3 mm or less for both overcoating and dual use.

以上の本実施形態の石膏組成物は、平均粒子径が５０μｍ以下の半水石膏及び炭酸カルシウム、並びに凝結遅延剤をそれぞれ特定の割合で含有するため、薄く平滑で表面硬度の高い塗膜を形成可能であり、かつ半水石膏の水和反応を抑制することが可能である。そのため、石膏組成物に水を加えて石膏系塗材としたときに、その石膏系塗材を乾燥硬化させることによって、引っ掻き傷や衝撃に対する耐性が良好な薄い塗膜でありながら、半水石膏の部分的又は不均一な水和反応が抑制され、ほぼ全体的又はほぼ均一に半水石膏が維持された塗膜を形成することが可能である。したがって、本実施形態の石膏組成物に水を加えた石膏系塗材によって、半水石膏の部分的又は不均一な水和反応に起因した色ムラが抑制された塗膜を形成することができる。   The gypsum composition of the present embodiment described above contains a half-water gypsum having an average particle size of 50 μm or less, calcium carbonate, and a setting retarder in specific ratios, so that a thin, smooth and high surface hardness coating film is formed. It is possible to suppress the hydration reaction of hemihydrate gypsum. Therefore, when water is added to the gypsum composition to form a gypsum-based coating material, the gypsum-based coating material is dried and cured, so that the gypsum-based gypsum composition is a thin coating film with good resistance to scratches and impacts. Thus, it is possible to form a coating film in which the partial or non-uniform hydration reaction is suppressed and the hemihydrate gypsum is maintained almost entirely or substantially uniformly. Accordingly, the gypsum-based coating material obtained by adding water to the gypsum composition of the present embodiment can form a coating film in which color unevenness due to partial or non-uniform hydration reaction of hemihydrate gypsum is suppressed. .

また、本実施形態の石膏組成物に主材として含有させる半水石膏及び炭酸カルシウムは、白色であるため、その石膏組成物に水を加えた石膏系塗材を用いることで、薄く平滑な漆喰調の塗膜を形成することが可能である。ここで、従来の漆喰系塗材を用いる場合では、漆喰系塗材のｐＨが塩基性の領域にあり、また、漆喰系塗材を塗布する作業中に粉塵が舞うこともある。さらに従来の漆喰系塗材を例えば石膏ボードに直接塗布すると、漆喰が石膏ボードに付着し難く、塗膜が石膏ボード表面に存在する石膏ボード用原紙から剥がれ落ちる場合や、石膏ボード用原紙の色が塗材を塗布した仕上がり面（例えば壁面）に色写りする場合がある。これに対して、本実施形態の石膏組成物を用いる場合、ｐＨが７以上９未満の石膏系塗材を容易に調製することが可能でより安全性が高まり、また、石膏ボードやクロス（壁紙）に対して付着しやすく、前述の色写りを防止することが可能である。そのため、本実施形態の石膏組成物及び石膏系塗材は、漆喰系塗材に比べて、建造物の内装壁や外装壁などのリフォームにより好適に用いられる。   Moreover, since the half-water gypsum and calcium carbonate to be contained as the main material in the gypsum composition of the present embodiment are white, by using a gypsum-based coating material obtained by adding water to the gypsum composition, a thin and smooth plaster It is possible to form a toned coating film. Here, in the case of using a conventional plaster-based coating material, the pH of the plaster-based coating material is in a basic region, and dust may fly during the operation of applying the plaster-based coating material. Furthermore, when a conventional plaster-based coating material is applied directly to a plasterboard, for example, the plaster is difficult to adhere to the plasterboard, and the paint film peels off from the plasterboard base paper present on the surface of the plasterboard, or the color of the baseboard for plasterboard May be colored on a finished surface (for example, a wall surface) coated with a coating material. On the other hand, when the gypsum composition of this embodiment is used, it is possible to easily prepare a gypsum-based coating material having a pH of 7 or more and less than 9, and the safety is further improved. ) And can prevent the above-mentioned color image. Therefore, the gypsum composition and the gypsum-based coating material of the present embodiment are preferably used for reforming an interior wall or an exterior wall of a building as compared with a plaster-based coating material.

なお、本実施形態の石膏組成物は、上述の通り、次の構成をとることが可能である。
［１］平均粒子径が５０μｍ以下の半水石膏と、平均粒子径が５０μｍ以下の炭酸カルシウムと、凝結遅延剤と、を含有し、前記半水石膏１００質量部に対して、前記炭酸カルシウムの含有量が１０〜４００質量部であり、前記凝結遅延剤の含有量が０．１質量部以上である、乾燥硬化形の塗材用石膏組成物。
［２］前記半水石膏の平均粒子径が４０μｍ以下であり、前記炭酸カルシウムの平均粒子径が４０μｍ以下である前記［１］に記載の石膏組成物。
［３］前記炭酸カルシウムの含有量が、前記半水石膏１００質量部に対して、１０〜２００質量部である前記［１］又は［２］に記載の石膏組成物。
［４］前記凝結遅延剤の含有量が、前記半水石膏１００質量部に対して、０．１〜１０質量部である前記［１］〜［３］のいずれかに記載の石膏組成物。
［５］前記凝結遅延剤の含有量が、前記半水石膏１００質量部に対して、０．１〜２質量部である前記［１］〜［４］のいずれかに記載の石膏組成物。
［６］前記凝結遅延剤が、クエン酸、コハク酸、酢酸、リンゴ酸、エチレンジアミン四酢酸、ジエチレントリアミン五酢酸、及びこれらの塩、並びにショ糖、澱粉、及びタンパク質分解物からなる群より選択される少なくとも１種である前記［１］〜［５］のいずれかに記載の石膏組成物。
［７］前記塗材用石膏組成物に水を加えて乾燥硬化させて塗膜としたときの粉末Ｘ線回折において、前記半水石膏の回折ピークを示し、前記半水石膏の水和反応に基づく二水石膏の回折ピークを示さない、前記［１］〜［６］のいずれかに記載の石膏組成物。
［８］前記塗材用石膏組成物に水を加えたときの水和反応の始発時間が２４時間以上である前記［１］〜［７］のいずれかに記載の石膏組成物。In addition, the gypsum composition of this embodiment can take the following structure as above-mentioned.
[1] A hemihydrate gypsum having an average particle diameter of 50 μm or less, calcium carbonate having an average particle diameter of 50 μm or less, and a setting retarder, and 100 parts by mass of the hemihydrate gypsum, A dry-curing gypsum composition for coating material, wherein the content is 10 to 400 parts by mass and the content of the setting retarder is 0.1 parts by mass or more.
[2] The gypsum composition according to [1], wherein the hemihydrate gypsum has an average particle size of 40 μm or less, and the calcium carbonate has an average particle size of 40 μm or less.
[3] The gypsum composition according to [1] or [2], wherein the content of the calcium carbonate is 10 to 200 parts by mass with respect to 100 parts by mass of the hemihydrate gypsum.
[4] The gypsum composition according to any one of [1] to [3], wherein a content of the setting retarder is 0.1 to 10 parts by mass with respect to 100 parts by mass of the hemihydrate gypsum.
[5] The gypsum composition according to any one of [1] to [4], wherein a content of the setting retarder is 0.1 to 2 parts by mass with respect to 100 parts by mass of the hemihydrate gypsum.
[6] The setting retarder is selected from the group consisting of citric acid, succinic acid, acetic acid, malic acid, ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, and salts thereof, and sucrose, starch, and proteolysate. The gypsum composition according to any one of [1] to [5], which is at least one kind.
[7] In powder X-ray diffraction when water is added to the gypsum composition for coating material and dried and cured to form a coating film, the diffraction peak of the hemihydrate gypsum is shown and the hydration reaction of the hemihydrate gypsum is performed. The gypsum composition according to any one of the above [1] to [6], which does not exhibit a diffraction peak of dihydrate gypsum based thereon.
[8] The gypsum composition according to any one of [1] to [7], wherein the initial time of the hydration reaction when water is added to the gypsum composition for coating material is 24 hours or more.

また、本実施形態の石膏系塗材は、次の構成をとることが可能である。
［９］平均粒子径が５０μｍ以下の半水石膏と、平均粒子径が５０μｍ以下の炭酸カルシウムと、凝結遅延剤と、水と、を含有し、前記半水石膏１００質量部に対して、前記炭酸カルシウムの含有量が１０〜４００質量部であり、前記凝結遅延剤の含有量が０．１質量部以上である、乾燥硬化形の石膏系塗材。
［１０］前記半水石膏、前記炭酸カルシウム、及び前記凝結遅延剤の合計１００質量部に対して、前記水を３０〜６０質量部含有する前記［９］に記載の石膏系塗材。
［１１］ｐＨが７以上９未満である前記［９］又は［１０］に記載の石膏系塗材。
［１２］乾燥硬化させて塗膜としたときの粉末Ｘ線回折において、前記半水石膏の回折ピークを示し、前記半水石膏の水和反応に基づく二水石膏の回折ピークを示さない、前記［９］〜［１１］のいずれかに記載の石膏系塗材。Moreover, the gypsum coating material of this embodiment can take the following structure.
[9] A hemihydrate gypsum having an average particle diameter of 50 μm or less, calcium carbonate having an average particle diameter of 50 μm or less, a setting retarder, and water, and with respect to 100 parts by mass of the hemihydrate gypsum, A dry-curing gypsum-based coating material having a calcium carbonate content of 10 to 400 parts by mass and a setting retarder content of 0.1 parts by mass or more.
[10] The gypsum-based coating material according to [9], containing 30 to 60 parts by mass of the water with respect to a total of 100 parts by mass of the hemihydrate gypsum, the calcium carbonate, and the setting retarder.
[11] The gypsum-based coating material according to [9] or [10], wherein the pH is 7 or more and less than 9.
[12] In powder X-ray diffraction when dried and cured to form a coating film, the diffraction peak of the hemihydrate gypsum is shown, and the diffraction peak of dihydrate gypsum based on the hydration reaction of the hemihydrate gypsum is not shown, [9] The gypsum-based coating material according to any one of [11].

＜石膏系塗材の施工方法＞
本発明の一実施形態の石膏系塗材の施工方法は、石膏系塗材を被着体に塗布する工程（以下、「塗布工程」と称することがある。）を含む。この施工方法において、石膏系塗材には、前述の実施形態に係る塗材用石膏組成物に水を加えて調製した乾燥硬化形の石膏系塗材、又は前述の実施形態に係る乾燥硬化形の石膏系塗材を用いる。そのため、前記塗布工程によって、半水石膏の状態が維持された塗膜を形成することができ、より具体的には、粉末Ｘ線回折測定において、石膏系塗材に含有されていた半水石膏の回折ピークを示し、かつ、その半水石膏の水和反応に基づく二水石膏の回折ピークを示さない塗膜を形成することが可能である。このような塗膜を形成できることから、本実施形態の石膏系塗材の施工方法は、石膏系塗材から形成される塗膜の色ムラを抑制することができ、石膏系塗材による塗膜の色ムラ防止方法として採用することができる。<Construction method of gypsum coating material>
The method for applying a gypsum-based coating material according to an embodiment of the present invention includes a step of applying a gypsum-based coating material to an adherend (hereinafter, also referred to as “application step”). In this construction method, the gypsum-based coating material is a dry-curing gypsum-based coating material prepared by adding water to the gypsum composition for coating material according to the above-described embodiment, or the dry-curing type material according to the above-described embodiment. Use a gypsum-based coating material. Therefore, the coating step can form a coating film in which the state of hemihydrate gypsum is maintained, and more specifically, in the powder X-ray diffraction measurement, hemihydrate gypsum contained in the gypsum-based coating material. Thus, it is possible to form a coating film that exhibits a diffraction peak of dihydrate gypsum based on the hydration reaction of the hemihydrate gypsum. Since such a coating film can be formed, the construction method of the gypsum-based coating material of the present embodiment can suppress uneven color of the coating film formed from the gypsum-based coating material, and the coating film by the gypsum-based coating material It can be employed as a method for preventing color unevenness.

本実施形態の施工方法では、上述の通り、石膏系塗材に前述の実施形態に係る塗材用石膏組成物に水を加えて調製した乾燥硬化形の石膏系塗材を用いることができる。そのため、本実施形態の施工方法は、前述の実施形態に係る塗材用石膏組成物に水を加えて乾燥硬化形の石膏系塗材を調製する工程（以下、「調製工程」と称することがある。）を含んでいてもよい。調製工程では、石膏組成物に、石膏組成物中の半水石膏、炭酸カルシウム、及び凝結遅延剤の合計１００質量部に対して、水を３０〜６０質量部添加することが好ましい。   In the construction method of this embodiment, as described above, a dry-cured gypsum-based coating material prepared by adding water to the gypsum composition for coating materials according to the above-described embodiment can be used. Therefore, the construction method of the present embodiment is a process of adding a water to the gypsum composition for coating materials according to the above-described embodiment to prepare a dry-cured gypsum coating material (hereinafter referred to as “preparation process”). May be included). In a preparation process, it is preferable to add 30-60 mass parts of water with respect to a total of 100 mass parts of hemihydrate gypsum in a gypsum composition, a calcium carbonate, and a setting retarder in a gypsum composition.

本実施形態の石膏系塗材を塗布する対象となる被着体（下地）は特に限定されない。被着体（下地）としては、例えば、セメント系及び石膏系素地、木質系素地、漆喰壁、各種プラスチック系素地、及び各種金属系素地などを挙げることができる。セメント系及び石膏系素地の具体例としては、石膏ボード、石膏プラスター、ドロマイトプラスター、コンクリート、土壁、珪藻土壁、パルプセメント板、及び木質系セメント板（木毛セメント板及び木片セメント板）などを挙げることができる。木質系素地の具体例としては、合板（ベニア板）、木質繊維板、及びパーティクルボードなどの木質ボード、単板積層材、並びに集成材などを挙げることができる。また、被着体（下地）は、クロスが貼着されたものでも、各種塗料が塗布されたものであってもよい。すなわち、本実施形態の施工方法によれば、前述の石膏系塗材をクロス（壁紙）や塗料の塗膜面上に塗布することによって、建造物の壁（内装壁及び外装壁）、床、及び天井などをリフォームすることが可能である。   The adherend (base) to which the gypsum-based coating material of this embodiment is applied is not particularly limited. Examples of the adherend (base) include cement-based and gypsum-based substrates, wood-based substrates, plaster walls, various plastic-based substrates, and various metal-based substrates. Specific examples of cement-based and gypsum-based substrates include gypsum board, gypsum plaster, dolomite plaster, concrete, earth wall, diatomaceous earth wall, pulp cement board, and wood-based cement board (wood wool cement board and wood chip cement board). Can be mentioned. Specific examples of the wood substrate include wood boards such as plywood (veneer boards), wood fiber boards, and particle boards, single board laminates, and laminated boards. In addition, the adherend (base) may be one to which a cloth is attached or one to which various paints are applied. That is, according to the construction method of the present embodiment, by applying the above-described gypsum-based coating material on the cloth (wallpaper) or paint coating surface, the walls of the building (interior wall and exterior wall), floor, It is possible to reform the ceiling and the like.

前記塗布工程において、石膏系塗材を被着体（下地）に塗布する際に用いる道具は、特に限定されないが、従来から塗り壁材に用いられている鏝（木鏝及び金鏝）などを用いることができる。塗布工程における被着体に対する石膏系塗材の塗布量は、１．０〜６．３ｋｇ／ｍ2であることが好ましい。また、被着体に対する石膏系塗材の塗り厚は、０．５〜３ｍｍであることが好ましい。In the application step, the tool used when applying the gypsum-based coating material to the adherend (base) is not particularly limited. Can be used. The coating amount of the gypsum coating material on the adherend in the coating step is preferably 1.0 to 6.3 kg / m 2 . Moreover, it is preferable that the coating thickness of the gypsum coating material with respect to a to-be-adhered body is 0.5-3 mm.

本実施形態の施工方法は、塗布工程の後、石膏系塗材の乾燥硬化によって形成された塗膜の上に、さらに、撥水性塗膜を設ける工程を含むことが好ましい。石膏系塗材による塗膜（石膏系塗膜）の上に撥水性塗膜を設けることにより、石膏系塗材による塗膜形成後において、塗膜に水分が吸収されることを抑制することができる。そのため、半水石膏の状態が維持された塗膜（より具体的には、粉末Ｘ線回折測定において半水石膏の回折ピークを示し、かつ、その半水石膏の水和反応に基づく二水石膏の回折ピークを示さない塗膜）を長期間に亘って安定して保持することが可能となる。   It is preferable that the construction method of the present embodiment further includes a step of providing a water-repellent coating film on the coating film formed by drying and curing the gypsum-based coating material after the coating process. By providing a water-repellent coating film on a gypsum-based coating film (gypsum-based coating film), it is possible to prevent moisture from being absorbed by the coating film after the gypsum-based coating film is formed. it can. Therefore, a coating film in which the state of hemihydrate gypsum is maintained (more specifically, dihydrate gypsum which shows a diffraction peak of hemihydrate gypsum in powder X-ray diffraction measurement and is based on the hydration reaction of the hemihydrate gypsum. It is possible to stably hold a coating film that does not show the diffraction peak of (2).

石膏系塗膜上に撥水性塗膜を設ける工程は、石膏系塗膜上に撥水性塗料を塗布することによって行うことができる。撥水性塗料としては、従来、漆喰や石膏プラスター、石膏ボード、けい酸カルシウム板などの上に塗布することで撥水性や防汚性を付与することができる種々の材料を用いることができる。また、市販の撥水性塗料を用いることもでき、その市販品としては、例えばＦＪ１５０、ＦＪ１７０、ＦＪ１７１、ＦＪ１７２（いずれもタイガレックス社製の商品名）などを挙げることができる。ＦＪ１７０、ＦＪ１７１、ＦＪ１７２などを用いれば油汚れ等に対する耐汚染性も付与することができる。   The step of providing a water-repellent coating on the gypsum-based coating can be performed by applying a water-repellent coating on the gypsum-based coating. As the water-repellent paint, conventionally, various materials that can impart water repellency and antifouling properties by applying on plaster, gypsum plaster, gypsum board, calcium silicate plate, and the like can be used. Commercially available water-repellent paints can also be used, and examples of the commercially available products include FJ150, FJ170, FJ171, and FJ172 (all are trade names manufactured by Taiga Rex). If FJ170, FJ171, FJ172 or the like is used, stain resistance against oil stains can be imparted.

なお、漆喰系塗材等の従来用いられている乾燥硬化形の塗材は、塗材を被着体に塗布してから２〜６時間経過すれば、さらに、撥水性塗膜等を設ける次工程を伴う場合であっても、十分な作業性を確保できる。本発明の一実施形態の石膏系塗材も従来の乾燥硬化形の塗材と同様、上記時間と同程度の時間で次工程を行うことができる。   In addition, a conventionally used dry-curing type coating material such as a plaster-based coating material is further provided with a water-repellent coating film after 2 to 6 hours have passed since the coating material was applied to the adherend. Even when a process is involved, sufficient workability can be ensured. The gypsum-based coating material according to one embodiment of the present invention can be subjected to the next step in the same time as the above-mentioned time, similarly to the conventional dry-curing type coating material.

本実施形態の石膏系塗材の施工方法は、次の構成をとることが可能である。
［１３］前記［１］〜［８］のいずれかに記載の塗材用石膏組成物に水を加えて調製した乾燥硬化形の石膏系塗材、又は前記［９］〜［１２］のいずれかに記載の乾燥硬化形の石膏系塗材を被着体に塗布する工程を含む、石膏系塗材の施工方法。
［１４］前記被着体に対する前記石膏系塗材の塗布量が、１．０〜６．３ｋｇ／ｍ2である前記［１３］に記載の施工方法。
［１５］前記被着体に対する前記石膏系塗材の塗り厚が、０．５〜３ｍｍである前記［１３］又は［１４］に記載の施工方法。
［１６］前記石膏系塗材による塗膜の上に、さらに撥水性塗膜を設ける工程を含む前記［１３］〜［１５］のいずれかに記載の施工方法。The construction method of the gypsum-based coating material of this embodiment can take the following configuration.
[13] A dry-cured gypsum coating material prepared by adding water to the gypsum composition for coating material according to any one of [1] to [8], or any of the above [9] to [12] A method for applying a gypsum-based coating material, comprising a step of applying the dry-curing gypsum-based coating material according to claim 1 to an adherend.
[14] The coating amount of the gypsum-based coating material to the adherend is, construction method according to the a 1.0~6.3kg / m 2 [13].
[15] The construction method according to [13] or [14], wherein a coating thickness of the gypsum-based coating material on the adherend is 0.5 to 3 mm.
[16] The construction method according to any one of [13] to [15], further including a step of providing a water-repellent coating film on the coating film made of the gypsum-based coating material.

以下、試験例を挙げて、本発明をさらに具体的に説明するが、本発明は以下の試験例に限定されるものではない。なお、以下の説明において、「部」及び「％」は、特に断らない限り質量基準である。   Hereinafter, although a test example is given and this invention is demonstrated further more concretely, this invention is not limited to the following test examples. In the following description, “parts” and “%” are based on mass unless otherwise specified.

＜漆喰組成物及び漆喰塗材の調製＞
漆喰組成物として、村樫石灰工業社製の商品名「村樫のしっくい（上塗）」を準備した。試験例１では、その漆喰組成物に混水率８０％で水を添加して（漆喰組成物１００部に水８０部を添加して）混練し、試験体１に用いる漆喰系塗材を調製した。<Preparation of plaster composition and plaster coating material>
As a stucco composition, a brand name “Muramura no plaster (coating)” manufactured by Murata Lime Industry Co., Ltd. was prepared. In Test Example 1, water is added to the stucco composition at a water mixing rate of 80% (80 parts of water is added to 100 parts of the stucco composition) and kneaded to prepare a stucco coating material used for the test body 1. did.

＜塗材用石膏組成物及び石膏系塗材の調製＞
試験例２〜２０では、試験体２〜２０に用いる塗材用石膏組成物として、表１〜４の上段（単位：質量部）に示す各成分を混合機で十分に混合撹拌して、各配合の塗材用石膏組成物を得た。凝結遅延剤としては、試験例２〜１７では市販の平均粒子径が２０μｍの粉末状のタンパク質分解物、試験例１８では平均粒子径が２０μｍのエチレンジアミン四酢酸二ナトリウム、試験例１９では平均粒子径が２０μｍのリンゴ酸ナトリウム、試験例２０ではジエチレントリアミン五酢酸を用いた。また、表１〜４には示していないが、試験体２〜２０に用いる塗材用石膏組成物には、塗材用石膏組成物（半水石膏、炭酸カルシウム、及び凝結遅延剤の合計）１００部に対して、糊剤（バインダー）としてエチレン−酢酸ビニル（ＥＶＡ）コポリマー（ワッカーケミカル社製、商品名「ＲＥ５４６Ｚ」）を５部配合した。
得られた各石膏組成物について、石膏組成物に混水率４０％で水を添加し（石膏組成物１００部に水４０部を添加し）、試験体２〜２０に用いる各石膏系塗材を調製した。試験例１９では、消石灰を用いて、石膏系塗材のｐＨを調整した。<Preparation of gypsum composition for coating material and gypsum-based coating material>
In Test Examples 2 to 20, each component shown in the upper part (unit: part by mass) of Tables 1 to 4 was sufficiently mixed and stirred with a mixer as the gypsum composition for coating materials used for Test Samples 2 to 20, A blended gypsum composition for coating materials was obtained. As the setting retarder, in Test Examples 2 to 17, a commercially available protein degradation product having an average particle size of 20 μm, in Test Example 18 disodium ethylenediaminetetraacetate having an average particle size of 20 μm, and in Test Example 19 the average particle size Is 20 μm sodium malate, and in Test Example 20, diethylenetriaminepentaacetic acid was used. Moreover, although not shown in Tables 1-4, the gypsum composition for coating materials used for the specimens 2 to 20 includes a gypsum composition for coating materials (total of hemihydrate gypsum, calcium carbonate, and setting retarder). To 100 parts, 5 parts of ethylene-vinyl acetate (EVA) copolymer (manufactured by Wacker Chemical Co., trade name “RE546Z”) was added as a paste (binder).
About each obtained gypsum composition, water is added to the gypsum composition at a water mixing ratio of 40% (40 parts of water is added to 100 parts of the gypsum composition), and each gypsum coating material used for the test bodies 2 to 20 is used. Was prepared. In Test Example 19, the pH of the gypsum-based coating material was adjusted using slaked lime.

＜試験体１〜２０の作製＞
調製した各塗材を、縦３０ｃｍ×横３０ｃｍの石膏ボード（ボード厚さ：９．５ｍｍ、吉野石膏社製、商品名「タイガーボード」）の表面に鏝で１ｍｍの厚さに塗り付けた。このときの塗材の塗布量は、石膏ボードの単位面積当たり、１．７ｋｇ／ｍ2とした。石膏ボードに塗布した塗材を、温度２３℃及び湿度５０％ＲＨで２４時間、乾燥硬化させて塗膜を形成した。塗膜が形成された各石膏ボードを４０℃の乾燥器内で、２４時間恒量乾燥して、それぞれ試験体１〜２０を作製した。<Preparation of Specimens 1-20>
Each of the prepared coating materials was applied to the surface of a plaster board (board thickness: 9.5 mm, manufactured by Yoshino Gypsum Co., Ltd., trade name “Tiger Board”) having a length of 30 cm and a width of 30 cm to a thickness of 1 mm. The coating amount of the coating material at this time was 1.7 kg / m 2 per unit area of the gypsum board. The coating material applied to the gypsum board was dried and cured at a temperature of 23 ° C. and a humidity of 50% RH for 24 hours to form a coating film. Each gypsum board on which the coating film was formed was dried for a constant time in a dryer at 40 ° C. for 24 hours to prepare test bodies 1 to 20, respectively.

＜評価＞
［ｐＨ］
試験体１に用いた漆喰組成物、並びに試験体２〜２０に用いた各石膏組成物について、各組成物１０ｇを採取し、それを２００ｍｌのイオン交換水に投入した。ｐＨメーター（東亜電液工業社製の商品名「ｐＨ ＭＥＴＥＲ ＨＭ-５Ｓ」）を使用して、組成物の投入３分後のｐＨを測定した。ｐＨの測定値から以下の基準にしたがって、評価した。各組成物を用いて測定したｐＨの値と、評価結果を表１〜４に示す。
Ａ：ｐＨが７．０以上８．０未満であった。
Ｂ：ｐＨが８．０以上９．０未満であった。
Ｃ：ｐＨが９．０以上であった。<Evaluation>
[PH]
About each plaster composition used for the test body 1 and each gypsum composition used for the test bodies 2-20, 10 g of each composition was extract | collected and it poured into 200 ml ion-exchange water. Using a pH meter (trade name “pH METER HM-5S” manufactured by Toa Denki Kogyo Co., Ltd.), the pH after 3 minutes from the introduction of the composition was measured. The pH was evaluated according to the following criteria from the measured value. The pH values measured using each composition and the evaluation results are shown in Tables 1 to 4.
A: The pH was 7.0 or more and less than 8.0.
B: The pH was 8.0 or more and less than 9.0.
C: The pH was 9.0 or more.

［表面粗さ］
表面粗さ測定機（ミツトヨ社製の商品名「ｓｕｆｔｅｓｔ ４０２」）を用いて、得られた試験体１〜２０のそれぞれについて、ＪＩＳ Ｂ０６０１：１９８２で規定される表面粗さを測定した。評価には、測定された十点平均粗さＲｚ（μｍ）を用い、以下の基準にしたがって、評価した。Ｒｚの値が低いほど試料における塗膜表面が平滑であることを表す。各試料のＲｚの値及び評価結果を表１〜４に示す。
Ａ：Ｒｚが２．０μｍ未満であった。
Ｂ：Ｒｚが２．０μｍ以上５．０μｍ未満であった。
Ｃ：Ｒｚが５．０μｍ以上であった。[Surface roughness]
The surface roughness specified by JIS B0601: 1982 was measured about each of the obtained test bodies 1-20 using the surface roughness measuring machine (Brand name "suftest 402" by Mitutoyo Corporation). For the evaluation, the measured ten-point average roughness Rz (μm) was used, and the evaluation was performed according to the following criteria. It represents that the coating-film surface in a sample is so smooth that the value of Rz is low. Tables 1 to 4 show Rz values and evaluation results of the respective samples.
A: Rz was less than 2.0 μm.
B: Rz was 2.0 μm or more and less than 5.0 μm.
C: Rz was 5.0 μm or more.

［表面硬度］
試験体１〜２０のそれぞれの塗膜表面について、ゴム硬度計（ＴＥＣＬＯＣＫ社製 ＴＹＰＥＤ）を用いて表面硬度を測定した。具体的には、各試験体における塗膜表面にゴム硬度計を押し付け、ＪＩＳ Ｋ６２５３−３：２０１２の規定に準拠したタイプＤデュロメータ硬さ（以下、「タイプＤ硬度」と記す。）を測定した。各試験体のタイプＤ硬度の測定値から、以下の基準にしたがって、評価した。各試験体の表面硬度及び評価結果を表１〜４に示す。
Ａ：タイプＤ硬度が５６以上であった。
Ｂ：タイプＤ硬度が５１以上５６未満であった。
Ｃ：タイプＤ硬度が５１未満であった。[surface hardness]
About each coating-film surface of the test bodies 1-20, surface hardness was measured using the rubber hardness meter (TYPEP by TECLOCK). Specifically, a rubber hardness meter was pressed against the coating film surface of each test specimen, and the type D durometer hardness (hereinafter referred to as “type D hardness”) in accordance with the provisions of JIS K6253-3: 2012 was measured. . From the measured value of type D hardness of each specimen, evaluation was made according to the following criteria. Tables 1 to 4 show the surface hardness and evaluation results of each specimen.
A: The type D hardness was 56 or more.
B: The type D hardness was 51 or more and less than 56.
C: Type D hardness was less than 51.

［Ｘ線回折］
各試験体における塗膜をＸ線回折し、二水石膏の有無を確認した。Ｘ線回折には、Ｘ線回折装置（島津製作所社製の商品名「ＬａｂＸ ＸＲＤ−６１００」）を用いた。試験体における塗膜表面全体を皮すきで削り取り、塗膜表面全体から削り取った塗膜粉末をＸ線回折装置の専用ホルダーに充填して、回折角度（２θ角度（θ：入射角））が１０°〜１６°の範囲で、粉末Ｘ線回折パターンを測定した。測定条件は、ターゲット：Ｃｕ、Ｆｉｌｔｅｒ：Ｎｉ、電圧：３０Ｖ、電流：１０ｍＡ、スキャニング速度：１°／ｍｉｎとした。[X-ray diffraction]
The coating film in each specimen was X-ray diffracted to confirm the presence of dihydrate gypsum. For X-ray diffraction, an X-ray diffractometer (trade name “LabX XRD-6100” manufactured by Shimadzu Corporation) was used. The entire surface of the coating film on the test body is scraped off, and the coating powder removed from the entire surface of the coating film is filled into a dedicated holder of an X-ray diffractometer, and the diffraction angle (2θ angle (θ: incident angle)) is 10. The powder X-ray diffraction pattern was measured in the range of from 16 ° to 16 °. The measurement conditions were: Target: Cu, Filter: Ni, Voltage: 30 V, Current: 10 mA, Scanning speed: 1 ° / min.

Ｘ線回折パターンにおいて、回折角１１〜１２°に二水石膏の明瞭なピークが表れ、回折角１４〜１５°に半水石膏の明瞭なピークが表れることが知られている。この事実から、得られたＸ線回折パターンにおいて、二水石膏が存在するか否か（すなわち、回折角１１〜１２°にピークを有するか否か）を確認するとともに、半水石膏が存在するか否か（すなわち、回折角１４〜１５°にピークを有するか否か）を確認した。表１〜４には、半水石膏のピーク及び二水石膏のピークのそれぞれの有無を示した。例として、図１に試験体２から採取した塗膜の粉末Ｘ線回折パターンを示し、図２に試験体１２から採取した塗膜の粉末Ｘ線回折パターンを示す。なお、試験体３〜１１及び１４〜２０から採取した各塗膜については、図１に示すような粉末Ｘ線回折パターンが確認され、試験体１３から採取した塗膜については、図２に示すような粉末Ｘ線回折パターンが確認された。   In an X-ray diffraction pattern, it is known that a clear peak of dihydrate gypsum appears at a diffraction angle of 11 to 12 °, and a clear peak of hemihydrate gypsum appears at a diffraction angle of 14 to 15 °. From this fact, in the obtained X-ray diffraction pattern, it is confirmed whether or not dihydrate gypsum is present (that is, whether or not there is a peak at a diffraction angle of 11 to 12 °), and hemihydrate gypsum is present. (That is, whether or not there is a peak at a diffraction angle of 14 to 15 °). Tables 1 to 4 show the presence or absence of hemihydrate gypsum peaks and dihydrate gypsum peaks. As an example, FIG. 1 shows a powder X-ray diffraction pattern of a coating film collected from the test body 2, and FIG. In addition, about each coating film extract | collected from the test bodies 3-11 and 14-20, the powder X-ray-diffraction pattern as shown in FIG. 1 is confirmed, and about the coating film extract | collected from the test body 13, it shows in FIG. Such a powder X-ray diffraction pattern was confirmed.

また、Ｘ線回折パターンにおいて、二水石膏のピークがあった場合、塗膜において、半水石膏の水和反応に基づく二水石膏の存在が示されたこととなる。この場合、半水石膏の部分的又は不均一な水和反応が生じるおそれがあることから、塗膜における色ムラの原因となり得ると評価し、表１〜４中の「色ムラの評価」欄に「×」と記した。逆に、Ｘ線回折パターンにおいて、二水石膏のピークがなかった場合、塗膜における色ムラを防止することが可能であると評価し、表１〜４中の「色ムラの評価」欄に「○」と示した。   Further, when there is a dihydrate gypsum peak in the X-ray diffraction pattern, the presence of dihydrate gypsum based on the hydration reaction of hemihydrate gypsum is shown in the coating film. In this case, since partial or non-uniform hydration reaction of hemihydrate gypsum may occur, it is evaluated that it may cause color unevenness in the coating film, and the “Evaluation of Color Unevenness” column in Tables 1 to 4 Is marked with "x". Conversely, in the X-ray diffraction pattern, when there was no dihydrate gypsum peak, it was evaluated that it was possible to prevent color unevenness in the coating film, and in the “Evaluation of color unevenness” column in Tables 1 to 4 “○” is shown.

Figure 2017099102
Figure 2017099102

Figure 2017099102
Figure 2017099102

Figure 2017099102
Figure 2017099102

Figure 2017099102
Figure 2017099102

以上の試験体１〜２０の評価結果より、平均粒子径が５０μｍ以下の半水石膏１００部、及び平均粒子径が５０μｍ以下の炭酸カルシウム１０〜４００部、並びに凝結遅延剤０．１質量部以上を含有する石膏組成物によって、薄く平滑でありながら、表面硬度が高く、かつ、色ムラを抑制すること可能な塗膜を形成できることが確認された（試験体２〜４、７〜１０、及び１４〜２０）。また、試験体２で用いた塗材用石膏組成物及び石膏系塗材における凝結遅延剤として用いたタンパク質分解物の代わりに、クエン酸ナトリウム、コハク酸ナトリウム、酢酸ナトリウム、ショ糖、澱粉をそれぞれ用いて、試験体２と同様にして各試験体を作製した。それらの各試験体に用いた石膏組成物のｐＨ、並びに各試験体の表面粗さ、表面硬度、及び粉末Ｘ線回折をそれぞれ上述の方法にて行ったところ、試験体２と概ね同程度の結果が得られたことが確認された。   From the evaluation results of the above test bodies 1 to 20, 100 parts of hemihydrate gypsum having an average particle diameter of 50 μm or less, 10 to 400 parts of calcium carbonate having an average particle diameter of 50 μm or less, and 0.1 part by weight or more of a setting retarder It was confirmed that a coating film that is thin and smooth and has high surface hardness and can suppress color unevenness can be formed by using the gypsum composition containing (test bodies 2 to 4, 7 to 10, and 14-20). In addition, instead of the proteolytic product used as a setting retarder in the gypsum composition for coating material and gypsum-based coating material used in Specimen 2, sodium citrate, sodium succinate, sodium acetate, sucrose, and starch were used. Each specimen was prepared in the same manner as specimen 2. When the pH of the gypsum composition used for each of the test specimens, and the surface roughness, surface hardness, and powder X-ray diffraction of each test specimen were measured by the above-described methods, they were approximately the same as those of the test specimen 2. It was confirmed that the result was obtained.

なお、炭酸カルシウムを含有しない石膏組成物を用いて作製した試験体６では、表面が粗い塗膜が形成されていた。この原因は、試験体６の作製において、石膏組成物に水を加えて調製した石膏系塗材を石膏ボードに塗布する際に、石膏系塗材に粘り気が生じ、鏝切れが悪かったためと考えられる。   In addition, in the test body 6 produced using the gypsum composition which does not contain calcium carbonate, the coating film with the rough surface was formed. This is thought to be due to the fact that when the gypsum coating material prepared by adding water to the gypsum composition was applied to the gypsum board in the preparation of the test body 6, the gypsum coating material became sticky and the fraying was poor. It is done.

半水石膏１００部に対して炭酸カルシウムを５００部含有する石膏組成物を用いて作製した試験体１１では、表面が粗く、表面硬度の低い塗膜が形成されていた。この原因は、試験体１１の作製において、石膏組成物に水を加えて調製した石膏系塗材を石膏ボードに鏝塗りした際に生じた鏝波が鏝押さえ作業によっても消え難かったためと考えられる。鏝波が消え難かった原因は、過量の炭酸カルシウムが、塗膜の形成過程で表層側に偏って存在し、形成途中にある塗膜の表層側がより硬くなっていたことによるものと推測される。   In the test body 11 produced using a gypsum composition containing 500 parts of calcium carbonate with respect to 100 parts of hemihydrate gypsum, a coating film having a rough surface and low surface hardness was formed. The cause of this is considered to be that the tsunami generated when the gypsum-based coating material prepared by adding water to the gypsum composition was applied to the gypsum board in the preparation of the test body 11 was difficult to disappear even by the pressing operation. . The reason why the tsunami was hard to disappear is presumed to be that an excessive amount of calcium carbonate existed on the surface layer side in the formation process of the coating film, and the surface layer side of the coating film in the process of formation was harder .

凝結遅延剤を含有しない石膏組成物を用いて作製した試験体１２、及び半水石膏１００部に対して凝結遅延剤を０．０７部含有する石膏組成物を用いて作製した試験体１３では、塗膜の粉末Ｘ線回折パターンにおいて、半水石膏及び二水石膏のそれぞれの回折ピークが確認された。したがって、試験体１２及び１３では、半水石膏が部分的に水和反応し、色ムラが生じやすい塗膜が形成されたことが示された。   In the test body 12 prepared using the gypsum composition containing no setting retarder and the test body 13 prepared using the gypsum composition containing 0.07 part of the setting retarder with respect to 100 parts of hemihydrate gypsum, In the powder X-ray diffraction pattern of the coating film, each diffraction peak of hemihydrate gypsum and dihydrate gypsum was confirmed. Therefore, in the test bodies 12 and 13, it was shown that hemihydrate gypsum partially hydrated and formed a coating film in which color unevenness was likely to occur.

また、試験体２〜４、７〜１０、及び１４〜２０に用いた各石膏系塗材については、ＪＩＳ Ａ６９０４に記載された標準軟度を針入り深さ２０±２ｍｍとして、その他はＪＩＳ Ａ６９０４に準じて水和反応の始発時間を２４時間及び４８時間まで測定した。その結果、２４時間経過後及び４８時間経過後のいずれにおいても、測定に用いた針の止まる位置は、石膏系塗材を入れた容器の底から０ｍｍであった。この結果と、上記の試験体を作製した際の石膏系塗材の塗り厚が３ｍｍ以下の薄塗りであることからも、上記の試験体では、石膏系塗材は水和反応することなく、石膏系塗材中の水分が被着体に吸収、かつ空気中に蒸発し、乾燥硬化による塗膜を形成したと考えられる。これは、石膏系塗材の水和反応の始発時間よりも乾燥硬化の完了時間がより早く、乾燥硬化による塗膜を形成したことを意味する。   Moreover, about each gypsum-type coating material used for the test bodies 2-4, 7-10, and 14-20, the standard softness described in JIS A6904 is set to the needle penetration depth 20 ± 2 mm, and others are JIS A6904. According to, the initial time of the hydration reaction was measured up to 24 hours and 48 hours. As a result, the position where the needle used for the measurement stopped was 0 mm from the bottom of the container containing the gypsum-based coating material after both 24 hours and 48 hours had elapsed. From this result and the coating thickness of the gypsum-based coating material when producing the above-described test body is a thin coating of 3 mm or less, in the above-mentioned test body, the gypsum-based coating material does not undergo a hydration reaction, It is considered that the moisture in the gypsum-based coating material was absorbed by the adherend and evaporated into the air to form a coating film by dry curing. This means that the completion time of drying and curing was earlier than the initial time of the hydration reaction of the gypsum-based coating material, and a coating film by drying and curing was formed.

Claims (16)

平均粒子径が５０μｍ以下の半水石膏と、
平均粒子径が５０μｍ以下の炭酸カルシウムと、
凝結遅延剤と、を含有し、
前記半水石膏１００質量部に対して、前記炭酸カルシウムの含有量が１０〜４００質量部であり、前記凝結遅延剤の含有量が０．１質量部以上である、乾燥硬化形の塗材用石膏組成物。Hemihydrate gypsum with an average particle size of 50 μm or less,
Calcium carbonate having an average particle size of 50 μm or less;
A set retarder, and
For 100 parts by mass of the hemihydrate gypsum, the content of the calcium carbonate is 10 to 400 parts by mass, and the content of the setting retarder is 0.1 parts by mass or more. Gypsum composition. 前記半水石膏の平均粒子径が４０μｍ以下であり、
前記炭酸カルシウムの平均粒子径が４０μｍ以下である請求項１に記載の塗材用石膏組成物。The hemihydrate gypsum has an average particle size of 40 μm or less,
The gypsum composition for coating material according to claim 1, wherein the calcium carbonate has an average particle size of 40 μm or less. 前記炭酸カルシウムの含有量が、前記半水石膏１００質量部に対して、１０〜２００質量部である請求項１又は２に記載の塗材用石膏組成物。   The gypsum composition for coating material according to claim 1 or 2, wherein a content of the calcium carbonate is 10 to 200 parts by mass with respect to 100 parts by mass of the hemihydrate gypsum. 前記凝結遅延剤の含有量が、前記半水石膏１００質量部に対して、０．１〜１０質量部である請求項１〜３のいずれか１項に記載の塗材用石膏組成物。   The gypsum composition for coating materials according to any one of claims 1 to 3, wherein a content of the setting retarder is 0.1 to 10 parts by mass with respect to 100 parts by mass of the hemihydrate gypsum. 前記凝結遅延剤の含有量が、前記半水石膏１００質量部に対して、０．１〜２質量部である請求項１〜４のいずれか１項に記載の塗材用石膏組成物。   The gypsum composition for coating material according to any one of claims 1 to 4, wherein a content of the setting retarder is 0.1 to 2 parts by mass with respect to 100 parts by mass of the hemihydrate gypsum. 前記凝結遅延剤が、クエン酸、コハク酸、酢酸、リンゴ酸、エチレンジアミン四酢酸、ジエチレントリアミン五酢酸、及びこれらの塩、並びにショ糖、澱粉、及びタンパク質分解物からなる群より選択される少なくとも１種である請求項１〜５のいずれか１項に記載の塗材用石膏組成物。   The setting retarder is at least one selected from the group consisting of citric acid, succinic acid, acetic acid, malic acid, ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, and salts thereof, and sucrose, starch, and protein degradation product. The gypsum composition for coating material according to any one of claims 1 to 5. 前記塗材用石膏組成物に水を加えて乾燥硬化させて塗膜としたときの粉末Ｘ線回折において、前記半水石膏の回折ピークを示し、前記半水石膏の水和反応に基づく二水石膏の回折ピークを示さない、請求項１〜６のいずれか１項に記載の塗材用石膏組成物。   In powder X-ray diffraction when water is added to the gypsum composition for coating material and dried and cured to form a coating film, a diffraction peak of the hemihydrate gypsum is shown, and two water based on the hydration reaction of the hemihydrate gypsum The gypsum composition for coating materials according to any one of claims 1 to 6, which does not show a diffraction peak of gypsum. 前記塗材用石膏組成物に水を加えたときの水和反応の始発時間が２４時間以上である請求項１〜７のいずれか１項に記載の塗材用石膏組成物。   The gypsum composition for coating material according to any one of claims 1 to 7, wherein the initial time of the hydration reaction when water is added to the gypsum composition for coating material is 24 hours or more. 平均粒子径が５０μｍ以下の半水石膏と、
平均粒子径が５０μｍ以下の炭酸カルシウムと、
凝結遅延剤と、
水と、を含有し、
前記半水石膏１００質量部に対して、前記炭酸カルシウムの含有量が１０〜４００質量部であり、前記凝結遅延剤の含有量が０．１質量部以上である、乾燥硬化形の石膏系塗材。Hemihydrate gypsum with an average particle size of 50 μm or less,
Calcium carbonate having an average particle size of 50 μm or less;
A set retarder;
Containing water,
A dry-curing gypsum-based coating in which the content of the calcium carbonate is 10 to 400 parts by mass and the content of the setting retarder is 0.1 parts by mass or more with respect to 100 parts by mass of the hemihydrate gypsum. Wood. 前記半水石膏、前記炭酸カルシウム、及び前記凝結遅延剤の合計１００質量部に対して、前記水を３０〜６０質量部含有する請求項９に記載の石膏系塗材。   The gypsum-based coating material according to claim 9, comprising 30 to 60 parts by mass of the water with respect to 100 parts by mass in total of the hemihydrate gypsum, the calcium carbonate, and the setting retarder. ｐＨが７以上９未満である請求項９又は１０に記載の石膏系塗材。   The gypsum-based coating material according to claim 9 or 10, having a pH of 7 or more and less than 9. 乾燥硬化させて塗膜としたときの粉末Ｘ線回折において、前記半水石膏の回折ピークを示し、前記半水石膏の水和反応に基づく二水石膏の回折ピークを示さない、請求項９〜１１のいずれか１項に記載の石膏系塗材。   In powder X-ray diffraction when dried and cured to form a coating film, the diffraction peak of the hemihydrate gypsum is shown, and the diffraction peak of dihydrate gypsum based on the hydration reaction of the hemihydrate gypsum is not shown. 11. The gypsum coating material according to any one of 11 above. 請求項１〜８のいずれか１項に記載の塗材用石膏組成物に水を加えて調製した乾燥硬化形の石膏系塗材、又は請求項９〜１２のいずれか１項に記載の乾燥硬化形の石膏系塗材を被着体に塗布する工程を含む、石膏系塗材の施工方法。   The dry-cured gypsum coating material prepared by adding water to the gypsum composition for coating material according to any one of claims 1 to 8, or the drying according to any one of claims 9 to 12. A method for applying a gypsum-based coating material, comprising a step of applying a cured gypsum-based coating material to an adherend. 前記被着体に対する前記石膏系塗材の塗布量が、１．０〜６．３ｋｇ／ｍ2である請求項１３に記載の施工方法。The construction method according to claim 13, wherein an amount of the gypsum coating material applied to the adherend is 1.0 to 6.3 kg / m 2 . 前記被着体に対する前記石膏系塗材の塗り厚が、０．５〜３ｍｍである請求項１３又は１４に記載の施工方法。   The construction method according to claim 13 or 14, wherein a coating thickness of the gypsum-based coating material on the adherend is 0.5 to 3 mm. 前記石膏系塗材による塗膜の上に、さらに撥水性塗膜を設ける工程を含む請求項１３〜１５のいずれか１項に記載の施工方法。   The construction method according to any one of claims 13 to 15, further comprising a step of providing a water-repellent coating film on the coating film made of the gypsum-based coating material.
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CN108367989B (en) 2021-09-03
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